CN103154093A - Saccharide siloxane copolymers and methods for their preparation and use - Google Patents

Abstract

A novel saccharide siloxane copolymer is useful in personal care compositions. The saccharide siloxane copolymer may be used as a universal emulsifier to prepare low odor emulsions for personal care applications.

Description

Sugar silicone copolymers and preparation and application thereof

The cross reference of related application and the statement of studying about federal government's fund assistance

Nothing.

Background technology

The sugar siloxanes is known in the art.It is found that, the sugared siloxanes that comprises hydroxyl-functional sugar component and organo-siloxane component is useful when being in application to hair, skin, fabric, paper wood, timber and other substrates.Sugar component can in one or more side extensions or terminal position or their certain combination, be covalently bond to organo-siloxane by key (including but not limited to ether, ester and amido linkage).

Summary of the invention

Sugar silicone copolymers (multipolymer) has formula:

R ² _aR ¹' _a’R ¹ _{(3-a-a ')}SiO-[(SiR ²R ¹O) _m-(SiR ¹ ₂O) _n(SiR ¹' R ¹O) _o] _y-SiR ¹ _{(3-a-a ')}R ¹' _a' R ² _aWherein

Each R ¹Can identical or different and each R ¹The alkyl, organic group or the formula R that comprise hydrogen, 1 to 12 carbon atom ³The group of-Q;

Q comprises epoxy group(ing), cycloalkyl epoxy base, primary amine or secondary amine, quadrol, carboxyl, halogen, vinyl, allyl group, acid anhydrides or mercapto functional group;

Each R ¹' be the long-chain organic group;

Subscript m has the mean value in 0 to 10,000 scope;

Subscript n have in 0 to 10,000 scope mean value and can be identical or different;

Subscript o has the mean value in 0 to 10,000 scope;

Each subscript a is 0,1,2 or 3 independently;

Each subscript a ' is 0,1,2 or 3 independently;

Subscript y makes this multipolymer have integer lower than 100 ten thousand molecular weight;

Each R ²Has formula Z-(G ¹) _b-(G ²) _c, and each copolymer molecule on average has at least one R ², wherein

G ¹For comprising the sugar component of 5 to 12 carbon atoms,

Amount (b+c) has the value of scope 1 to 10, and

Subscript b or subscript c can be 0,

G ²For comprising in addition by the sugar component of 5 to 12 carbon atoms of organic radical or organic silica-based replacement,

Each Z is for connecting base and being independently selected from:

-R ³-NHC(O)-R ⁴-、

-R ³-NHC(O)O-R ⁴-、

-R ³-NH-C(O)-NH-R ⁴-、

-R ³-C(O)-O-R ⁴-、

-R ³-O-R ⁴-、

-R ³-CH(OH)-CH ₂-O-R ⁴–、

-R ³-S-R ⁴-、

-R ³-CH(OH)-CH ₂-NH-R ⁴-、

-R ³-N(R ¹)-R ⁴-、

-NHC(O)-R ⁴-、

-NHC(O)O-R ⁴-、

-NH-C(O)-NH-R ⁴-、

-C(O)-O-R ⁴-、

-O-R ⁴-、

-CH(OH)-CH ₂-O-R ⁴–、

-S-R ⁴-、

-CH(OH)-CH ₂-NH-R ⁴-、

-N(R ¹)-R ⁴-、

-R ³-NHC(O)-、

-R ³-NHC(O)O-、

-R ³-NH-C(O)-NH-、

-R ³-C(O)-O-、

-R ³-O-、

-R ³-CH(OH)-CH ₂-O–、

-R ³-S-、

-R ³-CH(OH)-CH ₂-NH-、

-R ³-N(R ¹)-、

-R ³-N(R ⁸)-C(O)-R ⁴-、

-R ³-CH (OH)-CH ²-N (R ⁸)-R ⁴-or

-R ³-CH(N(R ⁴)(R ⁸))CH ₂OH；

Each R wherein ³With each R ⁴To comprise formula (R ⁵) _r(R ⁶) _s(R ⁷) _tThe divalence spacer groups of group,

Wherein at least one in subscript r, s and t is 1, and

Each R ⁵With each R ⁷The alkylidene group of 1 to 12 carbon atom independently,

Each R ⁶Wei – N (R ⁸)-, be R wherein ⁸Be selected from R ³, formula Z-X group, univalence hydrocarbyl or – N (H)-with the reaction product of epoxy-functional, cycloalkyl epoxy functional group, glycidyl ether functional group, anhydride functional group or lactone;

Each X is dibasic carboxylic acid, phosphate radical, sulfate radical, sulfonate radical or quaternary ammonium group independently, and

Precondition is

R ³And R ⁴In at least one must be present in described connection base, and

Each R ³With each R ⁴Can be identical or different.

Embodiment

Sugar silicone copolymers (multipolymer) comprises sugar component and silicone components.Silicone components forms the main chain of this copolymer molecule.Sugar component can be bonded to siloxane main chain in both at end group, side group or end group and side group.Perhaps, sugar component can be bonded to siloxane main chain in side group.

Under envrionment temperature and pressure condition, for example under 25 ℃ and 760mmHg, this multipolymer can be solid or liquid.This multipolymer is that solid or fluid (as liquid or glue) depend on many factors under envrionment conditions, comprises the polymerization degree (DP) of multipolymer.This multipolymer can have the DP in 2 to 15,000 or 5 to 10,000 or 50 to 5,000 or 100 to 1,000 or 50 to 1,000 or 50 to 500 or 100 to 400 scopes.This multipolymer can be used for personal care composition.

Perhaps, this multipolymer can be used as emulsifying agent.This multipolymer can be used as universal emulsifying agent, as being used for the emulsifying agent of water-in-oil (w/o) type emulsion (for example water-in-silicone type emulsion or organic water-in-oil emulsion).This multipolymer as universal emulsifying agent can be fluid under envrionment temperature and pressure condition.The viscosity of this fluid multipolymer depends on many factors, comprises the DP of this multipolymer.Can have DP in 2 to 500 or 5 to 500 or 25 to 500 or 50 to 450 or 100 to 400 or 50 to 350 scopes as this multipolymer of universal emulsifying agent.

This multipolymer has formula:

R ² _aR ¹’ _a’R ¹ _(3-a-a’)SiO-[(SiR ²R ¹O) _m-(SiR ¹ ₂O) _n(SiR ¹’R ¹O) _o] _y-SiR ¹ _(3-a-a’)R ¹’ _a’R ² _a。In the formula, each R ¹Can be identical or different.Each R ¹The alkyl, organic group or the formula R that comprise hydrogen, 1 to 12 carbon atom ³The group of-Q.Group Q comprises epoxy group(ing), cycloalkyl epoxy base, primary amine or secondary amine, quadrol, carboxyl, halogen, vinyl, allyl group, acid anhydrides or mercapto functional group.Each R ¹' for having the unit price organic group of at least 13 member's atoms.R ¹' can be alkyl, for example alkyl, thiazolinyl, alkynyl, aryl, alkaryl, cycloalkyl or cycloalkenyl group; Or ester functional group.Each R ¹' can be non-side chain or side chain.Each R ¹' can be saturated or part undersaturated.R ¹' be illustrated as the alkyl with average at least 14 carbon atoms.R for this type of alkyl ¹' be illustrated as the alkyl with 13 to 40 carbon atoms, Li such as – C ₁₃H ₂₇, – C ₁₄H ₂₉,-C ₁₅H ₃₁,-C ₁₆H ₃₃,-C ₁₇H ₃₅,-C ₁₈H ₃₇,-C ₁₉H ₃₉,-C ₂₀H ₄₁,-C ₂₁H ₄₃,-C ₂₂H ₄₅,-C ₂₃H ₄₇,-C ₂₄H ₄₉,-C ₂₅H ₅₁,-C ₂₆H ₅₃,-C ₂₇H ₅₅,-C ₂₈H ₅₇,-C ₂₉H ₅₉,-C ₃₀H ₆₁,-C ₃₁H ₆₃,-C ₃₂H ₆₅,-C ₃₃H ₆₇,-C ₃₄H ₆₉,-C ₃₅H ₇₁,-C ₃₆H ₇₃,-C ₃₇H ₇₅,-C ₃₈H ₇₇,-C ₃₉H ₇₉,-C ₄₀H ₈₁, and their combination.

Subscript m and n have the mean value in 0 to 15,000 or 0 to 10,000 or 0 to 500 scope separately, and described mean value can be identical or different.Subscript o has the mean value in 0 to 10,000 or 0 to 2,500 or 1 to 20 or 1 to 10 scope.Perhaps, subscript m can be greater than 0 to 1, and subscript n can be 40 to 65, and subscript o can be 5 to 25.Perhaps, for some application, for example when multipolymer will be as the emulsifying agent in some emulsion, the ratio of subscript m/(m+n+o) can be up to 0.05.Perhaps, the ratio of subscript m/(m+n+o) can be 0.001 to 0.05.The ratio of subscript n/(m+n+o) can be 0 to 0.989, and perhaps this ratio can be in from 0.15 to 0.989 scope.The ratio of subscript o/ (m+n+o) can be up to 0.8, and perhaps this ratio can be in from 0.01 to 0.8 scope.Subscript y, and at least one in subscript m and n can be greater than 0, make sugar component be in side group on multipolymer.

Each subscript a is 0,1,2 or 3 independently.Perhaps, each subscript a can be 0.When subscript a was 0, at least one in subscript m and n be greater than 0, and all sugar components are all in the side group on multipolymer (non-end group).Each subscript a ' can be 0,1,2 or 3; Perhaps, each subscript a ' can be 0 or 1.When each subscript a ' was 0, subscript o was greater than 0, and long-chain organic group R ¹' be the side group (non-end group) on multipolymer.Subscript y makes this multipolymer have integer lower than 100 ten thousand molecular weight.

Each R ²Has formula Z-(G ¹) _b-(G ²) _c, and each copolymer molecule on average has at least one R ²Group G ¹For comprising the sugar component of 5 to 12 carbon atoms.Subscript b or subscript c can be 0.Yet amount (b+c) has the value of scope from 1 to 10.Group G ²For comprising the sugar component of the carbon atom that is replaced by organic group or organosilicon radical in addition of 5 to 12." replacement " means hydrogen atom with carbon atom bonding by another substituting group, for example replaced by organic group or organosilicon radical.Each Z is for connecting base.

Each Z is independently selected from:

-R ³-NHC(O)-R ⁴-、-R ³-NHC(O)O-R ⁴-、-R ³-NH-C(O)-NH-R ⁴-、-R ³-C(O)-O-R ⁴-、

-R ³-O-R ⁴-、-R ³-CH(OH)-CH ₂-O-R ⁴–、-R ³-S-R ⁴-、-R ³-CH(OH)-CH ₂-NH-R ⁴-、-R ³-N(R ¹)-R ⁴-、-NHC(O)-R ⁴-、-NHC(O)O-R ⁴-、-NH-C(O)-NH-R ⁴-、-C(O)-O-R ⁴-、

-O-R ⁴-、-CH(OH)-CH ₂-O-R ⁴–、-S-R ⁴-、-CH(OH)-CH ₂-NH-R ⁴-、-N(R ¹)-R ⁴-、-R ³-NHC(O)-、

-R ³-NHC(O)O-、-R ³-NH-C(O)-NH-、-R ³-C(O)-O-、-R ³-O-、-R ³-CH(OH)-CH ₂-O–、-R ³-S-、

-R ³-CH (OH)-CH ₂-NH-,-R ³-N (R ¹)-,-R ³-N (R ⁸)-C (O)-R ⁴-,-R ³-CH (OH)-CH ₂-N (R ⁸)-R ⁴-or-R ³-CH (N (R ⁴) (R ⁸)) CH ₂OH.Perhaps, each Z is independently selected from :-R ³-N (R ⁸)-C (O)-R ⁴-,-R ³-CH (OH)-CH ₂-N (R ⁸)-R ⁴-, perhaps

-R ³-CH(N(R ⁴)(R ⁸))CH ₂OH。Each R ³With each R ⁴For comprising formula (R ⁵) _r(R ⁶) _s(R ⁷) _tThe divalence spacer groups of group.At least one in subscript r, s and t is 1.Each R ⁵With each R ⁷Be the alkylidene group of 1 to 12 carbon atom independently.Each R ⁶Wei – N (R ⁸)-, be R wherein ⁸Be selected from R ³, formula Z-X group, univalence hydrocarbyl or – N (H)-with the reaction product of epoxy-functional, cycloalkyl epoxy functional group, glycidyl ether functional group, diacetyl oxide functional group or lactone.R ⁸Suitable univalence hydrocarbyl can be alkyl or unsaturated alkyl.Work as R ⁸During for unsaturated alkyl, R ⁸It can be thiazolinyl.Thiazolinyl can have 2 to 12 carbon atoms, and its example is vinyl, allyl group, decene base and dodecenyl succinic.Perhaps, this thiazolinyl can have long chain, such as at least 14 carbon atoms.Work as R ⁸When being saturated hydrocarbyl, R ⁸It can be alkyl.This alkyl can be relatively short chain, such as 1 to 12 carbon atom.Perhaps, this alkyl can have long chain, such as at least 14 carbon atoms.Each X is carboxylate radical, phosphate radical, sulfate radical, sulfonate radical or the quaternary ammonium group of divalence independently.R ³And R ⁴In at least one must be present in described connection base.Each R ³With each R ⁴Can be identical or different.

The method for preparing this multipolymer

Above-mentioned multipolymer can be prepared by a method comprising the following steps: 1) make the reaction of the organopolysiloxane of functional organic and sugar moieties and produce sugared silicone copolymers as above and 2) if there is solvent, remove all or part of solvent.

Balance/condensation reaction

In one embodiment, step 1) undertaken by the method that comprises two steps.First step comprises balance and/or the condensation reaction of following composition

I) organopolysiloxane of short chain silanol functional,

Ii) amino dialkoxy alkyl silane,

Iii) has the long-chain organic group (R that is bonded to silicon ¹') alkyl-dialkoxysilanes, and

Iv) end blocking agent.

The product of first step is the organically-modified aminosiloxane of long-chain.

Composition (i) can have formula:

Wherein

Each R ¹⁰Be hydroxyl; Each R ¹¹Be univalence hydrocarbyl or R independently ¹⁰The value of subscript w is 0 to 10,000 or 0 to 50, and the value of subscript v is 0 to 10,000 or 0 to 50, and precondition is to work as R ¹¹All situations when being univalence hydrocarbyl, subscript w is greater than 0.Perhaps, the organopolysiloxane of short chain silanol functional can be silanol stopped.Perhaps, the organopolysiloxane of short chain silanol functional can be silanol stopped, and can not contain the silanol side group.Composition (i) can be two ends by the polydimethylsiloxane of silanol group end-blocking, and has from 2 to 50 or 2 to 20 DP.

Composition (ii) can have formula R ¹⁴R ¹³Si (OR ¹²) ₂Each R ¹²Be univalence hydrocarbyl independently, the alkyl of 1 to 4 carbon atom for example.Each R ¹³Be amido functional group, for example aminopropyl, aminoethylamino isobutyl-or aminoethylamino propyl group.Each R ¹⁴Be univalence hydrocarbyl independently, for example alkyl of 1 to 12 carbon atom, organic group or formula R ³The group of-Q, wherein R ³With Q as mentioned above.Perhaps, each R ¹⁴Be univalence hydrocarbyl independently, the alkyl of the alkyl of 1 to 12 carbon atom or 1 to 4 carbon atom for example.The example of composition (ii) is aminopropyl-methyl-dimethoxy silane; Aminoethylamino propyl group-methyl-dimethoxy silane; Aminoethylamino isobutyl--methyl-dimethoxy silane; And their combination.

Composition (iii) can have formula R ¹' R ¹⁴Si (OR ¹²) ₂Each R ¹', each R ¹²With each R ¹⁴As mentioned above.The example of composition (iii) is tetradecyl-methyl-dimethoxy silane; Hexadecyl-methyl-dimethoxy silane; Octadecyl-methyl-dimethoxy silane; Eicosyl-methyl-dimethoxy silane; And their combination.

Composition (iv) can be monoalkoxy silane, for example R ¹⁶ ₃SiOR ¹⁵Each R ¹⁶Be univalence hydrocarbyl, for example the alkyl or aryl of 1 to 8 carbon atom.Each R ¹⁵Can be hydrogen atom or univalence hydrocarbyl, for example the alkyl of 1 to 4 carbon atom.Perhaps, composition (iv) can be an end by the polydiorganosiloxane of a silanol base end-blocking, and for example an end is by the polydimethylsiloxane of a silanol base end-blocking.Composition (iv) can have formula

Each R wherein ¹⁷Be univalence hydrocarbyl independently, for example alkyl or aryl of 1 to 8 carbon atom, and subscript z is from 0 to 10,000 or 0 to 50 integer.Person of skill in the art will appreciate that during the organically-modified aminosiloxane of long-chain forms, can regulate that stoichiometry makes not is that all molecules all comprise amino.In this case, the product of the method is the combination that comprises above-mentioned multipolymer and organopolysiloxane.

In second step, the aminosiloxane that long-chain is organically-modified and sugar lactone reaction, thus form above-mentioned multipolymer.Sugar lactone (that is, glyconic acid lactone or another kind of lactone derived from sugar) and alkyl-modified aminosiloxane reaction.The example that is applicable to the glyconic acid lactone of second step has glucono-lactone (GL), erythronolactone, galactonolactone, glucono-lactone, mannonic acid lactone and ribose acid lactone.Other lactones derived from sugar can comprise glucuronolactone, glucoheptonic acid Inner ester, Portugal's octose acid lactone, isocitric acid lactone, saccharolactone and lactobionic acid lactone (LBL).Perhaps, this lactone can be GL or LBL.Be applicable to the commercially available acquisition of lactone of second step.

Glucose acid amide (Aldonamide) reaction

In an alternative embodiment, comprise for the preparation of the method for this multipolymer:

1) make the amine official energy organopolysiloxane and the sugar lactone that contain primary amine and secondary amine react to consume described primary amine,

2) make step 1) product and end-capping reagent react to seal secondary amine.

Step 1) and 2) can carry out successively.Perhaps, step 1) and step 2) can in conjunction with and carry out simultaneously.

Aforesaid method (and the additive method that forms the secondary amine copolymers containing hydroxyl and carboxyl groups herein) can also randomly comprise additional step.Additional step comprises makes secondary amine functional groups and end-capping reagent react to seal secondary amine functional groups.Secondary amine functional groups can be selected from aminopropyl, aminoethylamino propyl group and aminoethylamino isobutyl-.End-capping reagent can be lactone, can with secondary amine functional groups on halogenation unsaturated compound, epoxy functional compounds or the acid anhydrides of H-H reaction.

End-capping reagent can be lactone.Lactone can have following formula:

Each R ¹²Be hydrogen atom, hydroxyl, alkoxyl group or glycosyl independently.The example of alkoxyl group is methoxyl group, oxyethyl group, propoxy-and butoxy.Perhaps, each R ¹²Be hydroxyl or glycosyl.The scope of the value of subscript u is 5 to 12.Step 2) lactone that uses in is exemplified by above-mentioned sugar lactone.Perhaps, described lactone can be butyrolactone, ε caprolactone, γ glucono-lactone, δ glucono-lactone and LBL.Perhaps, lactone can be γ glucono-lactone or δ glucono-lactone.

Perhaps, end-capping reagent can be can with secondary amine on the halogenation unsaturated compound of atomic reaction of hydrogen.The halogenation unsaturated compound can be that the halogenation unsaturated hydrocarbons is such as the thiazolinyl muriate.Suitable thiazolinyl muriate can have 2 to 12 carbon atoms and can comprise vinylchlorid, chlorallylene, chlorodecane or chlorododecane.

Perhaps, end-capping reagent can be epoxy functional compounds.Epoxy functional compounds can be selected from allyl group epoxy functional compounds, cycloalkyl epoxy functional compound, glycidyl ether functional compound and Racemic glycidol.

Perhaps, end-capping reagent can be acid anhydrides.Acid anhydrides can have following formula:

Each R wherein ¹³Be univalence hydrocarbyl independently.Perhaps, each R ¹³Can be alkyl, such as the alkyl of 1 to 12 carbon atom.Suitable alkyl can be by methyl, ethyl, propyl group and butyl representative.Perhaps, acid anhydrides can comprise diacetyl oxide, sym-dichloroacetic anhydride, propionic anhydride, crotonic anhydride, methacrylic anhydride, butyryl oxide, isobutyric anhydride, diethylpyrocarbonate or 4-pentenoic acid anhydride.Perhaps, acid anhydrides can be diacetyl oxide.

Epoxy reaction

Perhaps, this multipolymer can be by comprising the method preparation that makes epoxy functionalized organopolysiloxane and N-alkylated glucamine such as N-METHYL-ALPHA-L-GLUCOSAMINE reaction.Epoxy functionalized organopolysiloxane can prepare by methods known in the art, and for example the composition by making the compound that comprises the epoxy that contains alkenyl functional and poly-organic radical hydrogen siloxane carry out hydrosilylation and prepare.The compound that contains the epoxy of alkenyl functional can be glycidyl allyl ether, dodecenyl succinic glycidyl ether, tetradecene base glycidyl ether or vaccenic acid base glycidyl ether.These compositions can be chosen wantonly and also comprise alkene, as undecylene.Perhaps, at first those skilled in the art can make N-alkyl-glycosamine and the compound of the epoxy that contains alkenyl functional react, and then carry out hydrosilylation reactions its product is connected to poly-organic radical hydrogen siloxane.

Perhaps, this multipolymer can be prepared by a method comprising the following steps:

1) make the epoxy compounds reaction of N-alkylated glucamine and alkenyl functional, and

2) make step 1) product and poly-organic radical hydrogen siloxane generation hydrosilylation.

In the method, step 1) and 2) can carry out successively.Perhaps, step 1) and step 2) can merge and carry out simultaneously.

In the method, the compound that contains the epoxy of alkenyl functional can be glycidyl allyl ether, lauryl diglycidyl ether, tetradecyl glycidyl ether or octadecyl glycidyl ether.The N-alkylated glucamine can be N-METHYL-ALPHA-L-GLUCOSAMINE.

Above-mentioned the whole bag of tricks can not use solvent or carry out under solvent exists.This solvent can be that alcohol is as methyl alcohol, ethanol, propyl alcohol, butanols or their combination.Perhaps, can with the organopolysiloxane of this functional organic (as, the organopolysiloxane of silanol functional, amine official can organopolysiloxane, epoxy functionalized organopolysiloxane or poly-organic radical hydrogen siloxane) be dissolved in solvent such as ethanol together with other compositions used in present method.After completing the method, can remove all or part of solvent, for example remove by stripping or distillation.Perhaps, if for example solvent is the composition that is suitable for emulsion (multipolymer will be formulated in wherein), complete during the method relief multipolymer stays solvent.

Perhaps, aforesaid method can carry out under the existence of oil.Can also add oil except solvent.Can make described component reaction add oil before preparing multipolymer.Perhaps, can add oil during the preparation multipolymer and/or afterwards and before removing any solvent.Perhaps, can add oil after removing a part of solvent.Perhaps, can add oil after removing whole solvents.When add oil can by those skilled in the art's root a tree name select to be used for preparing the expection end-use of reaction scheme, multipolymer of this multipolymer and selected oil whether with present method in any composition reaction used determine.For example, when oil is for example hydrocarbon, during such as alkane, Vaseline, squalane or mineral oil, can add earlier in the method oil because it will be can with other compositions reactions for the preparation of this multipolymer.When this multipolymer will be as emulsifying agent, maybe advantageously add oil before removing all solvents.

Aforesaid method can be undertaken by heating.Definite temperature depends on many factors, comprises selected concrete composition, yet temperature can be 50 ℃ to 100 ℃, and the reaction times of each step can be a few hours, and perhaps as many as is 10 hours, perhaps 1 to 10 hour.First of aforesaid method and second step can carry out successively.Perhaps, first and second step can in conjunction with and carry out simultaneously.

In aforesaid method, can use on reagent with organopolysiloxane on the functional group of molar excess of functional group reactions.For example, in the hydrosilylation of glycidyl allyl ether and SiH intermediate organopolysiloxane, use the glycidyl allyl ether mole number to the ratio of SiH mole number 1.1:1.Reagent can be greatly to 1.8:1 to the ratio of the functional group of siloxanes bonding.Perhaps, this mol ratio can be 1:1 to 1.8:1, perhaps 1.1:1 to 1.5:1.

Perhaps, calculate according to the amine value of amine official energy organopolysiloxane, sugar lactone can be 1:1 to the mol ratio of amine.Yet the sugared functional group in sugar lactone can be 0.5:1 to 2.0:1 to the mol ratio of the amine in amine official energy organopolysiloxane.

Comprise the organopolysiloxane that makes the short chain silanol functional and the polydimethylsiloxane (DOW of 5 centistokes for the preparation of the illustrative methods of multipolymer described herein

200 liquid), has the long-chain organic group (R that is bonded to silicon ¹') alkyl-dialkoxysilanes and amino dialkoxy alkyl silane mix, then with mixture heating up to 80 ℃.The gained reaction mixture can neutralize with the alkali of for example potassium hydroxide.Can add water after a few hours, and then heating (as, at the temperature of 120 ℃ to 150 ℃) a few hours.Can cooling gained reaction mixture, then use acid (for example Glacial acetic acid) neutralization.Can pass through coupling vacuum stripping, heating simultaneously (as, at the temperature of 120 ℃ to 150 ℃) a few hours remove volatile matter.Can filter products therefrom, to form the organically-modified aminosiloxane of long-chain.

The organically-modified aminosiloxane of long-chain can be with sugar lactone (for example δ-glucono-lactone) in the situation that exist alcohol by reacting in heating a few hours at the temperature of 40 ℃ to 75 ℃.Then optionally add other oil.The gained mixture can carry out air lift by heating (randomly under vacuum) at the temperature in the scope from 40 ℃ to 74 ℃.

Aforesaid method can not use solvent or carry out under solvent exists.Solvent can be the mounting medium that is applicable to personal care composition or solvent as herein described for example.Perhaps, can use alcohol, for example ethanol, propyl alcohol, butanols or their combination are carried out the method as solvent; And this solvent can be ethanol or propyl alcohol alternatively.After completing the method, can remove all or part of solvent, for example remove by stripping or distillation.Perhaps, if for example solvent is the mounting medium that is suitable for composition (multipolymer will be formulated in wherein), after completing the method, multipolymer can be stayed in solvent.

The definition of term and usage

The technical field of " personal care " is intended to comprise any Local treatment to any part of health, and this processing is intended to provide beneficial effect for this body portion.This beneficial effect can be directly or indirectly, and can be sense organ, mechanics, beauty treatment, protectiveness, preventative or curative.Although consider that human body is personal care composition of the present invention and by the desirable especially target substrate of the product of its preparation, but it will be apparent for a person skilled in the art that, have allied organization, especially other Mammalss of Keratin sulfate tissue such as skin and hair can be suitable target substrate and thereby the animal doctor to use be within the scope of the invention.

As the personal care composition that provides is adapted to provide beneficial effect for the part of health.As used herein, " being adapted to " means to allow safety and effectively applies beneficial effect to the mode of the part of health to prepare.As used herein, " safety and effective " means to provide to the human consumer who seeks this beneficial effect the amount of appreciable beneficial effect level, and does not damage the human consumer who is seeking this beneficial effect or it is caused significant discomfort.Significant discomfort is the discomfort that the beneficial effect that provides is provided, thereby ordinary consumer will be impatient at this discomfort.

The those of ordinary skill in personal care formulations field will understand that the expection that is used for selective basis unique individual care composition is used and the crowd of suitable basal component, optional additive and vehicle knows standard.the non-limitative example that can also be formulated into the additive in personal care composition except described multipolymer comprises: antiperspirant, other silicon, aerosol, antioxidant, sanitising agent, tinting material, other amendment, precipitation agent, ionogen, softener and oil, exfoliator, profoamer, perfume compound, wetting agent, occlusive agent, pediculicide, the pH control agent, pigment, sanitas, biocide, other solvents, stablizer, sun-screening agent, suspending agent, tanning agent, other tensio-active agents, thickening material, VITAMIN, plant-based medicine, wax, rheology modifier, antidandruff agent, anti-acne agents, anti-caries agent and wound healing promotor.

Be used for single the kind during product provides the personal care product of multiple beneficial effect in preparation, sacrifice some beneficial effect unrare.For example, with regard to hair, the increase of conditioning beneficial effect is accompanied by the reduction of hair " body " or volume usually.Add this multipolymer can allow to prepare these beneficial effects of combination and do not sacrifice the product of the effect of some beneficial effect, and really, in some preparations, it provides synergistic effect with regard to the combination of beneficial effect.The personal care product who prepares from the personal care composition that comprises multipolymer as herein described can strengthen and usually comes from the beneficial effect of the effect of antagonism each other, for example not only strengthens the conditioning beneficial effect but also strengthen curling maintenance beneficial effect.They also provide the thickening beneficial effect in hair, skin and color make-up.

In addition, the needs to some other additive can be eliminated or reduce to interpolation multipolymer described herein to personal care composition.For example, the one-tenth hydrogen bond property that has increase due to multipolymer as herein described, it is effective thickening material of ring-type silicon such as ring-type polymethyl siloxane (cyclomethicone), and thereby can reduce needs to other thickening additives, these other thickening additives may give by way of parenthesis the product property do not expected such as austerity, residue and form/or conditioning defective.

Multipolymer as herein described can be glue, waxy solid or solid under envrionment conditions.Yet be noted that the subdivision that has the multipolymer that occurs with liquid form, but the liquid discrete form can produce by the condition of handling such as temperature also.Yet, to realize making the range of viscosities that can form easily dispersion (for example solution or emulsion) for some multipolymer, at first multipolymer must come solubilising by being dissolved in suitable solvent or solvent blends.

The multipolymer of solubilising is used for forming solution or the emulsion of preparing to send into personal care composition subsequently.The suitability that concrete solvent blends is used expection based on ionic nature and this solvent of multipolymer is selected.In a specific embodiment, solvent blends comprises the mixture of paraffin and alcohol.Very in specific embodiment, alcohol comprises Virahol, 2-butyl-octanol or their combination at one.Perhaps, alcohol can comprise 2-butyl-octanol.

Term used herein " dispersion " means diphasic system, and wherein first-phase comprises distribution and spreads all over the final segmentation particle of the second body phase, and first-phase formation " interior " phase or disperse phase, and second formation " outward " phase or external phase.

Term used herein " solution " is intended to comprise mechanics dispersion, colloidal dispersion and true solution in a broad sense, and should not be construed and be confined to the latter.Solution is the dispersion that comprises homodisperse mixture, and wherein first-phase consists of solute and second-phase formation solvent.

Term used herein " emulsion " means to comprise the dispersion of the mixture of two kinds of immiscible fluids, is wherein consisting of the liquid suspension of the first disperse part under the help of emulsifying agent in the second external phase.

Except as otherwise noted, otherwise all quantity, ratio and per-cent all by weight.As used herein, article " ", " a kind of " and " described " refer to one (kind) or a plurality of (kinds) separately, unless indicated in addition by the application's context.

Composition

Above-mentioned multipolymer can be formulated in composition.Said composition comprises (A) above-mentioned multipolymer and (B) other composition.Other composition depends on the required end-use of selected concrete multipolymer and composition.

Said composition can be personal care composition.This personal care composition can comprise: (i) above-mentioned multipolymer, and optional (ii) is suitable for allowing the personal care composition part to be applied to the mounting medium of the part of health.Personal care composition is adapted to provide beneficial effect for the part of its health that applies.In addition, personal care composition can be chosen wantonly and comprise (iii) linking agent, and it is crosslinked that it is used for substrate crosslinked between multipolymer and/or that apply with said composition.Personal care composition can randomly comprise (iv) tensio-active agent.

It is known in the art being suitable for making the linking agent of crosslinking copolymers.In specific embodiment, crosslinkedly basically occur between the hydroxy functional group of sugar component.in embodiment more specifically, linking agent is optional from following non-limiting list: boric acid, boric acid ester (for example, boric acid three n-propyls, tri-isopropanolamine ring boric acid ester), alkylboronic acids or boric acid ester (phenyl-boron dihydroxide), titanic acid ester (for example, titanium isopropylate, two (acetylacetone based) metatitanic acid diisopropyl ester), zirconate, oxalic dialdehyde, glutaraldehyde, epoxy chloropropane, urea aldehyde, zirconium carbonate ammonium, the salt of polyvalent ion, difunctional epoxide or Racemic glycidol compound are (for example, 1, 4 butanediol diglycidyl ethers), two-(N-methylol) ureas, vulcabond (for example, tolylene diisocyanate, hexamethylene diisocyanate), 2-chloro-N, the N-diethyl acetamide, Trisodium trimetaphosphate, Phosphorus Oxychloride, propenal, the N-MU, dicarboxylic acid, two acyl chlorides, dialkyldichlorosilan,s (for example, dimethyldichlorosilane(DMCS)), the alkyl trichlorosilane (for example, METHYL TRICHLORO SILANE), reactive siloxane resin and their combination.Very in specific embodiment, linking agent comprises reactive siloxane resin or boric acid or boric acid ester at one.

Perhaps, this multipolymer can be used as dispersion and is delivered to personal care composition.Dilution or disperse this multipolymer can be easier to processing, and solvent that can suitable employing comprises polydimethylsiloxane, hydrocarbon and ethanol.Specially suitable solvent is annular siloxane, hydrocarbon-alcohol mixture, the pure and mild long-chain branch alcohol of long linear and water.

Due to this multipolymer and hydrocarbon, siloxanes and alcohol and with the consistency of water, they can be mixed in water base and non-water base personal care product, described personal care product provides beneficial effect for the part of health.The part of health comprises in the embodiment of hair therein, and this beneficial effect can comprise to be increased kindliness and keep hair moulding, fixed effect and enhancing gloss.

Emulsion

Find unexpectedly, compare with some previously known sugared siloxanes, above-mentioned multipolymer has the emulsifying property of improvement.In one embodiment, this multipolymer can be used as emulsifying agent.Emulsion with described multipolymer preparation can be used for personal care application.The amount of multipolymer in emulsion as emulsifying agent can be in greater than 0 to 10% or 0 to 5% or 1% to 2% scope.

Find unexpectedly, compare with some previously known sugared siloxanes, above-mentioned multipolymer has the emulsifying property of improvement.Thereby, can prepare and comprise described multipolymer as the emulsion of emulsifying agent.This emulsion can be water-in-oil (w/o) emulsion, comprises inner moisture water and outside comprises oil and as the external phase of the described multipolymer of emulsifying agent.Be not wishing to be bound by theory, it is believed that this emulsion does not need to comprise in addition the dispersion that any tensio-active agent except described multipolymer is kept interior phase.

In the external phase of this emulsion, oil used can be silicone oil or organic oil.This oil can be the silicone oil such as viscosity is the polydialkysiloxane of 1 to 350 centistoke.This type of silicone oil can be commercially available as following material from Michigan, USA Midland Dow Corning Corporation (Dow Corning Corporation (Midland, Michigan, U.S.A.)): DOW

200 liquid (its viscosity at 2 centistokes (cSt) to the scope of 350 centistokes), DOW

FZ-3196, DOW

244 liquid and DOW

245 liquid.The polydimethyl siloxane oil that derives from Dow Corning Corporation (Dow Corning Corporation) comprises that 244 liquid, 245 liquid and viscosity are 200 liquid of 2 centistokes, 5 centistokes, 10 centistokes, 20 centistokes, 50 centistokes, 100 centistokes or 350 centistokes.

Select as another kind, some organic oil is applicable to described emulsion.Suitable organic oil comprises ester, plant and/or mineral oil, hydrocarbon ils or Fatty Alcohol(C12-C14 and C12-C18).

Suitable ester comprises Isopropyl myristate, eight octyl pelargonates (octyl octanonanoate), decyl oleate, Wickenol 111, stearin, stearic acid ethylhexyl, IPIS, phenylformic acid C12-C15 alkane ester, coconut oil monooctyl ester, Wickenol 155, Tetradecyl lactate and Octyl adipate.The example of ester comprises that also (it can be used as Schercemol to the thylhexoic acid cetyl ^TMThe CO ester is purchased from Lubrizol Corp. of Ohio, USA Wyclif (Lubrizol Corporation (Wickliffe, Ohio, U.S.A.))) and glycerine three (thylhexoic acid) ester (it also can be used as Schercemol ^TMThe GTO ester is purchased from Lubrizol Corp. (Lubrizol)).

Suitable plant and mineral oil comprise Prunus amygdalus oil, wild Semen Armeniacae Amarum oil, Lipoval A, Viscotrol C, Oenothera oil, Jojoba oil, sunflower oil, sweet oil, wheatgerm oil and mineral oil.

Suitable hydrocarbon ils comprises Vaseline, mineral oil, squalene, capric acid/Trivent OCG; The alkane of at least 12 carbon atoms.For example, long chain alkane (as have the alkane of at least 12 carbon atoms, and as Permethyl 99A. or isohexadecane) can be used as organic oil.

Suitable Fatty Alcohol(C12-C14 and C12-C18) comprises stearyl alcohol, hexadecanol.

This emulsion can be scattered in oil above-mentioned multipolymer by comprising, the method for then adding described water prepares.Water progressively can be added into oil phase, and mix between twice interpolation.Can make the water of gained and the combination of oil phase stand high-shear.Oil forms mutually outside or external phase.Mixing can be for example intersects agitator (cross stirrer) by use and carries out with 700 to 1,000 rev/mins (rpm) mixing when adding water.After adding water, the mixture that can choose wantonly gained further mixes for some time with 1,000 to 2,000rpm, as 1 second to 10 minutes, and perhaps 1 minute to 5 minutes.For example, the mixing condition after adding whole waters can comprise with 1,000rpm and mixing 1 minute, then mixes 5 minutes with 2,000rpm.

Useful specific installation carries out high shear mixing, and this equipment makes can be with very high shear-mixed emulsion to reduce the viscosity of granularity and increase emulsion.High shear mixing can be improved the stability of emulsion.High shear mixing can be with commercially available high-shear device for example such as can be from the commercially available T25 DigitalULTRA-of IKA company (IKA, Wilmington (North Carolina, U.S.A.)) of Wilmington, North Carolina

And so on homogenizer or such as carrying out from the homogenizer the commercially available L4RT of English Silverson Mechanology Inc. (Silverson Machines Ltd. (England)).The precise conditions of high shear mixing will depend on the factor such as the emulsion initial viscosity and change to some extent, yet the example of shear conditions has with 7,000 to 8, and 000rpm mixed this emulsion 1 second to 1 minute, perhaps 15 seconds.

One of ordinary skill in the art will appreciate that needs easily to form required emulsion always.Emulsion as herein described and other emulsions are subject to similar constraint.That is, they are thermodynamic instabilities, need the input energy to cause emulsifying effect.It may be enough carrying out simple stirring by mixing, perhaps can use more senior shearing means, comprises the employing high-shear device.Perhaps, can use the reversing method.

Form the necessary stirring extent of emulsion and may need to adopt mixing device.Mixing device provides required energy input usually.The non-limitative example that belongs to these mixing devices of shearing scope comprises: 1) with impeller, and for example water screw, the oblique container of leaf oar, straight oar, Rushton oar or Cowles blade; 2) kneading type agitator, for example, Bake Perkins agitator (Baker-Perkins); 3) utilize the normotopia in-migration that passes the aperture to produce the high-shear device of shearing, for example, homogenizer, sonolator or microfluidizer; 4) utilize the high-shear device of rotor and stator structure, for example colloidal mill, homomic continuous mill (line mill), from the homogenizer of IKA or Bematek; 5) has the continuous compounding machine of list or twin screw; What 6) have internal impeller or a rotor/stator device changes pot type agitator, for example Turello agitator; With 7) centrifugal stirrer, for example Hauschild high speed agitator.The combination of mixing device can also provide beneficial effect, for example the container with impeller can be connected to high-shear device.High-shear device is known in the art and commercially available acquisition, for example high-shear device can be such as can be from (IKA (the Wilmington of IKA company of Wilmington, North Carolina, North Carolina, U.S.A.)) commercially available T25 Digital ULTRA-

And so on the homogenizer high-shear mixer that maybe can obtain from English Silverson Mechanology Inc. (Silverson Machines Ltd. (England)).

The selection of mixing device is based on the type of the interior phase for the treatment of emulsification.For example, can use high-shear device emulsification mutually in low viscosity, the positive displacement in aperture is passed in described high-shear device utilization.Yet, with regard in high viscosity mutually with regard to, rotor/stator device, twin screw compounding device or to change the pot type agitator be often better selection.

Composition order of addition in the emulsion preparation can be determined by experience.For example, the desirable order of addition of thickness phase emulsification can be: (a) described multipolymer and oil are merged; (b) follow shearing progressively to add the water that comprises water until form thick phase emulsion; And randomly, (c) follow shearing, further be diluted to desired concn with other oil and/or other oil phase.The method optionally further comprises adds other composition, such as the following describes those.

Emulsion with described multipolymer preparation can be used for the personal care product.Thereby the method can be chosen wantonly and also comprise with described emulsion preparation personal care product.The personal care product can have to the part of its health that applies certain combination of cosmetology function, treatment function or these functions.the conventional example of this series products includes but not limited to: antiperspirant and reodorant, protective skin cream, the skin care lotion, wetting Agent for Printing Inks, facial treatment agent is as removing acne agents or winkle removing agent, personal cleanser and facial cleansing agent, bathe oil, perfume, Gulong perfume, face powder, sun-screening agent, the front use that shaves and the rear lotion of using that shaves, shaving soap and shaving foam, shampoo, hair conditioner, hair coloring agents, hair is straight along agent, hair jelly, mousse, gelifying agent, agent for permanent hair waving, trichogen and stratum corneum coating, makeup, color make-up, foundation cream, hide free time cream, kermes, lipstick, eyeliner, Mascara, removers, the color make-up remover, the wrinkle weighting agent, skin defect is hidden agent, the skin surface smooth agent, the eyelash curler herbal leaven, nail varnish, the hair cosmetic product, eye shadow, health cosmetic agent, and pulvis, medicine frost cream, paste or sprays (comprise anti-acne agents, the tooth hygiene agent, microbiotic, accelerator for concrescence, nutrition agent etc., it can be preventative and/or curative).Generally speaking, the personal care product can prepare with the carrier that can be convenient to so that any conventionally form applies, and described form includes but not limited to liquid, irrigation, washing lotion, cream frost, paste, gel, foam, mousse, ointment, spray, aerosol, soap, rod, soft solid, solid gel and gel.The formation of suitable carrier is that those of ordinary skills obviously know.

In a specific embodiment, prepare the water-in-oil emulsion sample according to following universal program.By emulsifying agent and oil are mixed with oil phase.Described oil is Isopropyl myristate or DOW

200 liquid, DOW

200 liquid are that viscosity is the silicone oil of 5 centistokes, and it can be commercially available from Dow Corning Corporation (Dow Corning Corporation).Described emulsifying agent is above-mentioned multipolymer.In every kind of oil phase, oil phase contains 10% emulsifying agent and 90% oil.By with water and the water of sodium-chlor with 39:1 to 99:1: the NaCl weight ratio mixes to prepare water.Perhaps, water can comprise water: sodium-chlor: the weight ratio of glycerine is water, sodium-chlor and the glycerine of 74:1:5 to 92.5:1.25:6.25.For every kind of sample, water progressively is added into oil phase.Between each the interpolation, with sample at DAC150 FlackTek ^TMSpeedMixer ^TM(commercially available in the FlackTek of South Carolina, United States Lan Delong company (FlackTek, Inc. (Landrum, South Carolina, U.S.A.)) with 3400 rev/mins of (rpm) centrifugal for some time so that thick emulsion to be provided.

After having added whole waters, at homogenizer (T25 Digital ULTRA-

Commercially available from the IKA of Wilmington, North Carolina company (IKA (Wilmington, North Carolina, U.S.A.))) in shear to provide miniemulsion with 〉=7,000rpm to the thick emulsion of gained.

With the weighing scale of emulsion, water can 20 % by weight to 95 % by weight or the amount of 40 to 90 % by weight or 60 % by weight to 80 % by weight exist.

Personal care application

Above-mentioned emulsion can be used for personal care application.When above-mentioned emulsion was used for personal care application, this emulsion can also comprise other composition, described above those.described other composition can be selected from other silicon, aerosol, antioxidant, sanitising agent, tinting material, other amendment, precipitation agent, ionogen, softener and oil, exfoliator, profoamer, perfume compound, wetting agent, sealing agent, pediculicide, the pH control agent, pigment, sanitas, biocide, other solvents, stablizer, sun-screening agent, suspending agent, tanning agent, other tensio-active agents, thickening material, VITAMIN, plant-based medicine, wax, rheology modifier, antiperspirant, antidandruff agent, anti-acne agents, anti-caries agent and wound healing promotor, oil in addition, hydrophilic medium, weighting agent, fiber, film-forming polymer, other tensio-active agent and/or emulsifying agent, dyestuff, structurizing reagent, activeconstituents, perfume compound, sanitas and their combination.Perhaps, described other composition can be selected from other oil, hydrophilic medium, weighting agent, fiber, film-forming polymer, other tensio-active agent and/or emulsifying agent, dyestuff, structurizing reagent, activeconstituents (for example personal care promoting agent), perfume compound, sanitas or their combination.

Oil in addition

Oil in addition can be the another kind of oil that is selected from above-mentioned oil, and perhaps described oil can be selected from alkyl oil, silicone oil and fluorinated oil.Described oil can be selected from ethereal oil and nonvolatile oil and their mixture.

For present patent application, term " alkyl oil " means basically by carbon atom and hydrogen atom, and may go back aerobic and nitrogen-atoms forms or even by carbon atom and hydrogen atom, and may go back aerobic and nitrogen-atoms forms, and the oil of not siliceous or fluorine atom; It may contain ester, ether, amine or amide group.

For present patent application, term " silicone oil " means to contain at least one Siliciumatom, perhaps contains the oil of ≡ Si-O-group.

For present patent application, term " fluorinated oil " means to contain the oil of at least one fluorine atom.

For present patent application, term " ethereal oil " means under room temperature and normal atmosphere, is less than the oil (or non-aqueous media) that can evaporate in one hour at contact skin.Ethereal oil can be the volatility cosmetic oil, it is at room temperature liquid, particularly have the non-zero vapour pressure under room temperature and normal atmosphere, especially have 0.13Pa to 40000Pa(10～3 to 300mmHg) or 1.3Pa to 13000Pa(0.01 to 100mmHg) or 1.3Pa to 1300Pa(0.01 to 10mmHg) vapour pressure.

In addition, ethereal oil under atmospheric pressure has the boiling point of 150 ℃ to 260 ℃ or 170 ℃ to 250 ℃ usually.

This emulsion can comprise the volatile hydrocarbon base oil, and this alkyl oil especially is selected from the alkyl oil that flash-point is 40 ℃ to 102 ℃ or 40 ℃ to 55 ℃ or 40 ℃ to 50 ℃.

With respect to the gross weight of this emulsion, this ethereal oil can 0.1 % by weight to 80 % by weight, perhaps 1 % by weight to 70 % by weight, and perhaps the amount of 5% to 50 % by weight is present in emulsion.

This emulsion can comprise at least a nonvolatile oil in mutually at non-volatile liquid fat.With respect to the gross weight of non-volatile liquid fat phase, nonvolatile oil can 0.1 % by weight to 80 % by weight, perhaps 0.5 % by weight to 60 % by weight, and perhaps the amount of 1 % by weight to 50 % by weight exists.

Optional alkyl oil (the side chain C8-C16 alkane particularly from containing 8 to 16 carbon atoms of volatile hydrocarbon base oil, the C8-C16 isoalkane (also referred to as isoparaffin) of petroleum origin for example, for example Permethyl 99A. is (also referred to as 2,2,4,4,6-five methylheptane), isodecane and isohexadecane, those oil of for example selling with commodity Isopar or Permethyl), C8-C16 ester and PIVALIC ACID CRUDE (25) dissident ester and their combination of side chain.

Also spendable ethereal oil comprises volatility silicon, for example volatile straight chain or ring-type silicone oil, particularly viscosity≤8 centistokes (8 * 10 ⁶m ²/ s) and especially containing those of 2 to 7 Siliciumatoms, these silicon can be chosen wantonly and comprise alkyl or the alkoxyl group that contains 1 to 10 carbon atom.

Volatile fluorated solvent such as Nonafluoromethoxybutcompositions or trifluoromethyl-cyclopentane also are suitable in said composition.

The fixed hydrocarbon base oil includes but not limited to phytogenous alkyl oil, and as three esters of lipid acid and glycerine, the lipid acid of this three ester can have the various chain lengths of 4 to 24 carbon atoms, and these chains may be straight or brancheds, and are saturated or unsaturated.these oily examples have wheatgerm oil, sunflower oil, raisin seed oil, sesame oil, Semen Maydis oil, apricot oil, Viscotrol C, shea butter, Lipoval A, sweet oil, soybean oil, sweet almond oil, plam oil, rapeseed oil, Oleum Gossypii semen, hazelnut oil, Macadamia nut oil, Jojoba oil, clover oil, poppyseed oil, pumpkin-seed oil, pepo oil, blackcurrant oil, Oenothera oil, millet oil, large wheat oil, the lamb's-quarters wheat oil, rye-seed oil, Thistle oil, lumbang oil, passionflower oil or musk rose oil, or sad and/or Triglyceride DDD, the synthetic ether that contains 10 to 40 carbon atoms, non-polar hydrocarbon base oil (for example squalene), straight or branched hydrocarbon (as whiteruss, liquid petroleum gel and naphtalene oil), hydrogenation or partially hydrogenated polyisobutene, Isoeicosane, squalane, decene/butylene copolymer and polybutene/polyisobutene co-polymer and poly decene, and their mixture, synthetic ester, formula R ' COOR for example " oil, wherein R ' representative comprises the fatty acid residue of the straight or branched of 1 to 40 carbon atom, and R " represent the especially hydrocarbyl chain that comprises 1 to 40 carbon atom of branch, precondition is R '+R "〉10, sad 16-stearyl for example, Isopropyl myristate, Wickenol 111, the phenylformic acid alkyl ester of 12 to 15 carbon atoms, lauric acid hexyl ester, Wickenol 116, isononyl isononanoate, palmitinic acid 2-(ethyl hexyl) ester, the isostearyl isostearate ester, sad alcohol ester or sad polyol ester, decylate or ricinoleate ester (for example two sad propylene glycol esters), hydroxylation ester, for example different stearyl ester of lactic acid or the different stearyl ester of oxysuccinic acid two, and pentaerythritol ester, be the Fatty Alcohol(C12-C14 and C12-C18) of liquid under room temperature, its have contain 12 to 26 carbon atoms branch and/or undersaturated carbon back chain, for example Standamul G, isooctadecanol, oleyl alcohol, 2-hexyl decyl alcohol, 2-butyl octanol or 2-undecyl pentadecylic alcohol, higher fatty acid is as oleic acid, linolic acid or linolenic acid, carbonic ether, acetic ester, citrate, and their combination.

Non-volatile silicone oil can be: non-volatile polydimethylsiloxane (PDMS); The polydimethylsiloxane that comprises alkyl or alkoxy base, these groups are that hang and/or the end that be in the silicon chain of side, and these groups respectively contain 3 to 40 carbon atoms; Phenyl silicon; The optional poly-alkyl methyl siloxanes of fluoridizing; With the polysiloxane of lipid acid, Fatty Alcohol(C12-C14 and C12-C18) or polyoxyalkylene modification, and their combination.The alkyl methyl siloxanes, it has formula Me usually ₃SiO[Me ₂SiO] _A[MeR " ' SiO] _BSiMe ₃, R wherein " ' for containing the alkyl of 6 to 30 carbon atoms, the Me represent methylidene, the polymerization degree (DP) is that the scope of A and B sum is 3 to 50.The volatile matter of alkyl methyl siloxanes and liquid substance both all can be used for described composition.

Select as another kind, this oil can comprise silicon methyl alcohol.These materials are described in WO 03/101412 A2, and can usually be described as the hydrocarbyl functional siloxane fluid or the resin that replace.

It is 650 to 10,000g/mol oil that this emulsion can contain molar mass, and described oil can be selected from: lipophilic polymer such as polybutene; Polyisobutene, for example Parleam; Poly decene and Nexbase 2004; Vinylpyrrolidone copolymer such as vinyl pyrrolidone/cetene multipolymer (MM=7300g/mol); Ester such as total carbon atom number order are 35 to 70 straight-chain fatty acid ester, for example tetramethylolmethane four pelargonates; Hydroxylated ester such as Polyglycerine-2 three isostearates; Aromatic ester such as tridecyl alcohol trimellitate; And pentaerythritol ester, and three Isoeicosanes alcohol citrate, the different pelargonate of tetramethylolmethane four, glycerine three isostearates, glycerine three (2-decyl) four decylates, pentaerythritol tetraoctyl stearate, Polyglycerine-2 tetraoctyl stearate and their combination.

This emulsion can comprise fluid silicon compound such as silica gel or full-bodied silicone oil.

Can select the viscosity under 25 ℃ is 10 to 10,000,000 centistoke or 1,000 to 2,500,000 centistoke or 5,000 to 1,000, the polydimethylsiloxane of 000 centistoke or 10,000 to 60,000 centistokes.

The weight-average molecular weight of fluid silicon can be for 1,000 to 1,500,000g/mol or 200,000 to 1,000,000g/mol.

The oil phase of this emulsion also can contain and is closed in silicone elastomer gel, the elastomerics SOLID ORGANIC polysiloxane of fat in mutually, and wherein at least a elastomerics SOLID ORGANIC polysiloxane is at least part of crosslinked.The example of this elastomerics SOLID ORGANIC polysiloxane is described in following patent and patent announcement: US 5654362, EP 848029, EP 869142, WO2007109240, WO2007109260, WO2007109282, WO2009006091, WO2010080755, US4,987,169 and US5760116.These elastomer gels can be non-emulsification or self-emulsifying or the combination of these two.

Hydrophilic media

The water of this emulsion can comprise hydrophilic media, this hydrophilic media comprises the mixture of water or water and hydrophilic organic solvent, and described hydrophilic solvent is for example alcohol straight or branched low-grade monobasic alcohol (for example ethanol, Virahol or n-propyl alcohol) and the polyvalent alcohol (for example glycerine, Glycerol dimer, propylene glycol, sorbyl alcohol, pentanediol and polyoxyethylene glycol) of 2 to 5 carbon atoms (as contain) or wetting ability C2 ether and C2-C4 aldehyde.

With respect to the gross weight of emulsion, the mixture of water or water and hydrophilic organic solvent can 0.1 % by weight to 95 % by weight or the amount of 10 % by weight to 80 % by weight be present in emulsion.

Weighting agent

The weighting agent that is applicable to emulsion described herein can be mineral or organically, have any form (microplate shape, spherical or rectangular), no matter crystallography form (such as flake crystalline, regular crystal, hexagonal crystal, iris etc.).example comprises talcum powder, mica, silicon-dioxide, kaolin, polymeric amide, poly--Beta-alanine powder and polyethylene powders, tetrafluoroethylene polymer powder, lauroyl Methionin, starch, boron nitride, polymeric hollow microsphere, acrylic copolymer, the silicone resin microballon, elastomerics organopolysiloxane particle, precipitated chalk, magnesiumcarbonate, secondary magnesium phosphate, hydroxyapatite, hollow silica microsphere, glass or ceramic microcapsule and metallic soap be Zinic stearas for example, Magnesium Stearate, lithium stearate, zinc laurate or magnesium myristate, the polymethylmethacrylate powder.Perhaps, weighting agent can be polyurethane powder.

Perhaps, weighting agent can be elastomerics organopolysiloxane powder.Advantageously, this elastomerics organopolysiloxane is non-emulsification.Spherical Projectiles gonosome organopolysiloxane is described in following patent application: JP-A-61-194 009, EP-A-242 219, EP-A-295 886 and EP-A-765 656.Can also announce United States Patent (USP) 7,399, other mix particles described in 803 with the organopolysiloxane powder and as patent.

Elastomerics organopolysiloxane powder can comprise at least a silicone resin that is coated with, as is coated with the elastomerics organopolysiloxane powder of silsesquioxane resins, as for example patent US 5,538, described in 793.

Other elastomerics organopolysiloxanes of spherical powder form can be with the fluoro-alkyl group functionalization mix Si powder or with phenyl group functionalized mix Si powder.

Weighting agent can be N-acylamino acid powder.The N-acylamino acid can comprise the acyl group that contains 8 to 22 carbon atoms, for example 2-ethyl hexyl acyl group, caproyl, lauroyl, nutmeg acyl group, palmitoyl, stearyl-or cocoyl.Amino acid can be for example Methionin, L-glutamic acid or L-Ala.

When existing, weighting agent can be added into emulsion with the amount of 0.01 % by weight to 30 % by weight.

Fiber

For present patent application, term " fiber " means to have the object of length L and diameter D, makes L much larger than D, and D is that the square section of wherein this fiber is by the circular diameter of inscribe.

Specifically, the ratio (or shape factor) of L/D is 3.5 to 2500 or 5 to 500 or 5 to 150.

The fiber that can be used for described emulsion can be the fiber with synthetic or natural, mineral or organic origin.The fiber that can be used for described emulsion is optional from polymeric amide, Mierocrystalline cellulose, PPTA or polyethylene fibre.Also can use polyethylene fibre.

Fiber can 0.01 % by weight to 10 % by weight amount be present in emulsion.

Film-forming polymer

Some film-forming polymer can be jelling agent.For present patent application, term " film-forming polymer " means to contain the compound of at least two repeating units or at least three repeating units, wherein said compound can be own or forms the upper continuous film of macroscopic view at (particularly on keratin material) on upholder under the existence of complementary membrane-forming agent, or cohesion film or have makes force of cohesion that described film can separate from described upholder and the film of mechanical property.

In one embodiment, film-forming polymer is to be selected from following film forming organic polymer: dissolve in the film-forming polymer of organic liquid medium, when organic liquid medium comprises at least a when oil, particularly lipophilic polymer; Can be scattered in the film-forming polymer in organic solvent medium, particularly with the nonaqueous dispersion of polymer particle, the polymkeric substance of the dispersion form in preferred silicone oil or alkyl oil.

Perhaps, the film-forming polymer that can be used in emulsion can comprise the polymkeric substance of the synthetic polymer of free radical type or bunching thing type, natural origin and their mixture.This film-forming polymer comprises acrylic polymers, polyamide polymer and multipolymer and the polyisoprene of acrylic polymers, urethane, polyester, polymeric amide, polyureas, cellulose-based polymer (for example nitrocotton), silicon polymer (particularly silicone resin), silicon grafting.

According to composition of the present invention can comprise grafting ethylenic polymer particle at described fat the dispersion in mutually as film-forming polymer.

The silicon-base macromolecule monomer that can serve as membrane polymer comprises the polydimethylsiloxane that contains list (methyl) acrylate end group.Operable silicon-base macromolecule monomer comprises monomethyl acryloxy propyl group polydimethylsiloxane.

Perhaps, this emulsion can contain linearity block ethylenic polymer (hereinafter referred to as " block polymer ") as film-forming polymer.For present patent application, term " block polymer " means to comprise the polymkeric substance of at least two kinds of different blocks, preferred at least three kinds of different blocks.

This polymkeric substance can be the polymkeric substance of linear structure.Perhaps, can use the polymkeric substance of nonlinear organization, for example branch, star, polymkeric substance grafting or other structures.

In one embodiment, film-forming polymer comprises at least three kinds of different blocks, and the first and second block phase objectionable interminglings of this block polymer.

In one embodiment, film-forming polymer is to dissolve in the organic film-forming polymer of fat in mutually, and described fat comprises the liquid phase that contains at least a oil mutually.

Fat-soluble film-forming polymer can have any chemical type and especially can be selected from: a) alkene, cycloolefin, divinyl, isoprene, cinnamic, vinyl ether, ester or fat-soluble, amorphous homopolymer and multipolymer acid amides or (methyl) acrylate or acid amides, described (methyl) acrylate or acid amides comprise straight chain, side chain or the cyclic alkyl of 4 to 50 carbon atoms, and it can be unbodied.described fat-soluble homopolymer and multipolymer can obtain from being selected from following monomer: (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) vinylformic acid isopentyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) methyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid tridecane ester and (methyl) stearyl acrylate ester or their combination.

Spendable concrete fat-soluble multipolymer comprises: i) contain silicon main chain and acrylic resin grafts or contain the acrylic resin main chain and the acrylic resin of silicon grafts-silicon graftomer, as being sold with trade(brand)name SA 70.5 by 3M company and at patent US 5,725,882, US 5,209, and 924, US 4,972,037, US 4,981,903, US 4,981, and 902 and US 5,468,477 and patent US 5,219,560 and EP 0 388 582 in the product described; Ii) belong to a kind of lipophilic polymer that carries the fluoro group in above-mentioned classification, particularly patent US 5,948, the Fomblin product and patent EP 0 815 836 and the US 5 that describe in 393, alkyl (methyl) acrylate/perfluoroalkyl (methyl) acrylate copolymer of describing in 849,318; Iii) by olefinic type monomers polymerization or copolymerization and the polymkeric substance or the multipolymer that obtain, described ethene belongs to monomer and comprises one or more ethylenic linkages, and it can be conjugation (or diene).For the polymkeric substance or the multipolymer that are obtained by olefinic type monomers polymerization or copolymerization, might be to use vinyl, acrylic acid series or methacrylic acid based copolymer.

In one embodiment, film-forming polymer is the segmented copolymer that comprises at least one block that is comprised of styrene units or styrene derivatives (for example vinyl toluene, chloro-styrene or 1-chloro-4-methyl-benzene).

in one embodiment, film-forming polymer is selected from vinyl ester, and (vinyl is connected directly to the saturated of the Sauerstoffatom of ester group and 1 to 19 carbon atom that this vinyl ester has the carbonyl that is connected to ester group, the straight or branched hydrocarbyl group) and the multipolymer of at least a other monomers, described other monomers can be vinyl ester (non-already present vinyl ester), alpha-olefin (containing 8 to 28 carbon atoms), alkyl vinyl ether (alkyl that contains 2 to 18 carbon atoms) or allyl group or methylallyl ester (the saturated straight or branched hydrocarbyl group that contains 1 to 19 carbon atom of the carbonyl that is connected to ester group).

These multipolymers can be partial cross-linked with linking agent, described linking agent can be the vinyl type or allyl group or methylallyl type, as tetraallyl oxygen base ethane, Vinylstyrene, suberic acid divinyl ester, dodecanedioic acid divinyl ester and octadecane diacid divinyl ester.

The fat-soluble film-forming polymer that can also mention comprises fat-soluble multipolymer, those that obtain as the copolymerization by the copolymerization of the vinyl ester that contains 9 to 22 carbon atoms or alkyl acrylate or alkyl methacrylate (as described in alkyl group contain 10 to 20 carbon atoms).

This lipoid soluble copolymer is optional from polyvinyl stearate, with Vinylstyrene, with diallyl ether or with the multipolymer of the crosslinked polyvinyl stearate of diallyl phthalate, poly-(methyl) stearyl acrylate ester copolymer, polyoxyethylene lauryl vinyl acetate and poly-(methyl) lauryl acrylate multipolymer, and these gather (methyl) acrylate may be crosslinked with Ethylene glycol dimethacrylate or dimethacrylate TEG ester.

Unbodied fat-soluble polycondensate, preferably not comprising anyly provides hydrogen interactional group, particularly contain the aliphatic polyester of C4-50 alkyl group side chain or the polyester that the condensation of lipid acid dimer obtains or the polyester that even comprises the silica-based segment of block, grafting or end group form, as definition in patent application FR 0 113 920.

The unbodied fat-soluble polysaccharide that comprises alkyl (ether or ester) side chain particularly contains the alkylcellulose of saturated or undersaturated straight or branched C1 to C8 alkyl group, as ethyl cellulose and propyl cellulose.

Perhaps, film-forming polymer can be selected from cellulose-based polymer such as nitrocotton, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate or ethyl cellulose, or be selected from urethane, acrylic polymers, vinyl polymer, polyvinyl butyral acetal class, Synolac, derived from the resin of acetal product, as aryl sulfonic acid amides-formaldehyde resin (for example toluol sulfonamide-formaldehyde resin) and aryl sulfonic acid amides epoxy resin.

Perhaps, film-forming polymer can be silicone resin.For present patent application, term " resin " means three-dimensional structure.In one embodiment, silicone resin is selected from silsesquioxane and siloxysilicate material.In one embodiment, silicone resin is selected from siloxysilicate material, trimethylsiloxy silicon ester for example, and it can be expressed from the next: [R ¹⁶ ₃SiO _1/2] _E(SiO _4/2) _F(unit M and Q), wherein subscript E and F can have 50 to 80 value independently of one another, and R ¹⁶Represent alkyl, as the alkyl of methyl or two or more carbon atoms.Unit M can be 0.7 to 1 with the ratio of unit Q.

Perhaps, silicone resin optional self-contained as shown in the formula the silsesquioxane of T unit: [R ¹⁷SiO _3/2] _G, wherein have can thousands of value and the R of as many as for subscript G ¹⁷Represent alkyl, for example the alkyl of methyl or two or more carbon atoms.In one embodiment, silsesquioxane is selected from poly methyl silsesquioxane, and it is such as R ¹⁷Silsesquioxane (poly-propyl group silsesquioxane) for methyl or propyl group and so on.Poly methyl silsesquioxane can comprise and for example be less than 500 T unit, perhaps 50 to 500 T unit.

In one embodiment of the invention, the silicone resin solubilized maybe can be scattered in silicone oil or volatile organic liquid.In one embodiment, silicone resin is solid under 25 ℃.

In one embodiment, silicone resin can have 1,000 to 10,000g/mol molecular weight.

In another embodiment, the film forming silicone resin is multipolymer, and wherein at least one unit of this multipolymer is selected from silicon unit M, D, T and Q, and wherein at least one the other unit in this multipolymer is selected from ester.

Non-limiting, film-forming polymer is optional from following polymkeric substance or multipolymer: urethane, polyurethane-acrylate resinoid, polyureas, polyureas-urethane, polyester-polyurethane, polyethers-urethane, polyester, polyesteramide, alkyd; Acrylic resin and/or vinyl polymer or multipolymer; Acrylic resin-siliceous copolymer; Polyacrylamide; Silicon polymer (for example silicon polyurethane or silica acrylic acid resinoid) and fluorinated polymer, and their mixture.

Film-forming polymer can be the vinyl polymer that comprises at least one carbon siloxanes dendrimers base unit.This vinyl polymer can especially have main chain and at least one side chain, and described side chain comprises carbon siloxanes dendrimers structure.For present patent application, term " carbon siloxanes dendrimers structure " expression is with the molecular structure of high molecular branch group, has in the radial direction a height rule what begin from the main chain key.This carbon siloxanes dendrimers structure in Unexamined Patent Japanese patent application Kokai9-171154 with the formal description of the siloxanes of height cladodification-silyl alkylidene group multipolymer.

This vinyl polymer can be a kind of in the polymkeric substance of describing in the example of patent application EP 0 963 751, or the polymkeric substance that obtains according to the method that described patent application is described.

According to an embodiment, vinyl polymer can also comprise at least one organic fluorine group.Fluorine-containing vinyl polymer can be a kind of in the polymkeric substance of describing in the example of patent application WO 03/,045 337, or a kind of in the polymkeric substance that obtains according to the method that described patent application is described.

According to an embodiment, the grafted ethene based polyalcohol is present in oil, and described oil can be volatile, is selected from silicone oil and/or alkyl oil.According to an embodiment, described silicone oil can be cyclopentasiloxane.Perhaps, described alkyl oil can be Permethyl 99A..Emulsion can comprise at least a polyamide polymer or multipolymer, it is optional from polymeric amide homopolymer, the polymeric amide with aliphatic chain branch, polymeric amide-organo-siloxane, polymeric amide-polyester copolymer and polymeric amide-polyacrylic copolymer, and their mixture.

For the polyamide polymer that can be used in described emulsion, can also mention the polymeric amide that comprises at least one polyorganosiloxane group, contain 1 to 1,000 organo-siloxane unit in main chain or with the grafts form.This polyamide polymer is those that for example describe in document US-A-5 874 069, US-A-5 919 444, US-A-6 051 216, US-A-5 981 680 and WO 04/,054 524.

This emulsion can comprise semi-crystalline polymer, and it can have the fusing point greater than or equal to 30 ℃.This melting point values is corresponding to the 5 or 10 ℃ of fusing points measured that raise with differential scanning calorimeter (DSC) such as the calorimeter of being sold with trade(brand)name DSC 30 by Mei Tele company (Mettler), temperature per minute.(fusing point of considering be in corresponding Thermogram the point of the temperature of high endotherm(ic)peak).This semi-crystalline polymer comprises at least one crystallizable side chaining or at least one crystallizable block.Except described crystallizable chain or block, this polymer blocks is unbodied.For the present invention, term " crystallizable chain or block " means when independent, depends on higher than fusing point or lower than fusing point, will reversibly become chain or the block of crystalline state from metamict.For the present invention, chain is for being that hang or the one group of atom side of side for main polymer chain.Block is the one group of atom that belongs to main chain, this group consist of polymer repeat unit one of them.The example that can be used for semi-crystalline polymer of the present invention has the polyolefin block copolymer of controlled crystallization, and monomer whose is described in EP-A-O 951 897.

Film-forming polymer can be present in emulsion with the amount of 0.1 % by weight to 30 % by weight when existing.

Other surfactants/emulsifiers

This emulsion can also comprise other tensio-active agent or emulsifying agent.Other tensio-active agent or emulsifying agent at room temperature may be solid, and it can be independent block polymer, graftomer and/or unregulated polymer or two or more combination in them.The graftomer that may mention has been the grafting silicon polymer of hydrocarbyl chain and grafting the hydrocarbyl polymers of silicon chain.

Thereby, can use the grafting-block or the segmented copolymer that comprise at least one organopolysiloxane type block and at least one free radical polyalcohol block, for example the graft copolymer of acrylic resin/silicon type, especially can use when described non-aqueous media contains silicon.

Also might use the grafting-block or the segmented copolymer that comprise at least one organopolysiloxane type block and at least one polyether block.Should poly-organopolysiloxane block can be polydimethylsiloxane or poly-(C2 – C18) alkyl methyl siloxanes; This polyether block can be poly-(C2 – C18) alkylidene group, for example polyoxyethylene and/or polyoxypropylene.Particularly, can use dimethicone copolyol or (C2 – C18) alkyl dimethicone copolyol.

Water-soluble or water dispersible silicon polyether composition can be included in emulsion of the present invention.These also are called polyoxyalkylene siliceous copolymer, silicon poly-(oxyalkylene) multipolymer, silicon diol multipolymer or Silicon surfactant.These can be straight chain, shape or material graft type of rake, or ABA type, wherein B is the siloxane polymer block, A is poly-(oxyalkylene) group.Should can be formed by the polyethylene oxide/polypropylene oxide group of polyoxyethylene, polyoxytrimethylene or mixing by poly-(oxyalkylene) group.Other oxide compounds are also possible as oxybutylene or phenylene oxide.The silicon polyether composition that can be included in the another type in the present composition is the ABn polyoxyalkylene siliceous copolymer of describing as in EP 0 492 657.

Described other emulsifying agent or tensio-active agent can be selected from nonionogenic tenside, anion surfactant, cats product and amphoterics or their combination.Can be with reference to " the Encyclopedia of Chemical Technology " of Kirk-Othmer, volume 22, pp.333-432,3rd edition, 1979, Wiley(" encyclopedia of chemical technology ", the 22nd volume, the 333-432 page, the 3rd edition,, Valleylad Inc. in 1979) about the definition about anion surfactant, amphoterics and nonionogenic tenside of the 347-377 page of the definition, particularly this reference of the character of tensio-active agent and (emulsification) function.

Nonionogenic tenside can comprise: the ether oxyethylation of glycerine and/or oxypropylation (it can comprise 1 to 150 oxygen ethene and/or oxypropylene group); Oxyethylation and/or ether oxypropylation (it can comprise 1 to 150 oxygen ethene and/or oxypropylene group) of Fatty Alcohol(C12-C14 and C12-C18) (especially C8-C24 or C12-C18 alcohol), as contain the cetearyl alcohol alcohol ether (CTFA title Ceteareth-30(ceteareth-30) of the oxyethylation of 30 oxyethylene groups groups) and comprise the oxyethylation ether (CTFA title C12-15 Pareth-7(C12-15 alkanol polyethers-7) of the mixture of the C12-C15 Fatty Alcohol(C12-C14 and C12-C18) that 7 oxyethylene groups roll into a ball); The fatty acid ester of polyoxyethylene glycol (its can comprise 1 to 150 ethylene glycol unit) (for example C8-C24 or C16-C22 acid), for example PEG-50 stearate and PEG-40 monostearate; The fatty acid ester of glyceryl ether oxyethylation and/or oxypropylation (it can comprise 1 to 150 oxygen ethene and/or oxypropylene group) (especially C8-C24 acid, preferred C16-C22 acid), for example PEG-200 glyceryl monostearate; With the stearin of 30 oxyethylene group reunion ethoxylations, with the olein of 30 oxyethylene group reunion ethoxylations, with the coconut oil glyceryl ester of 30 oxyethylene group reunion ethoxylations, with the Tegin ISO of 30 oxyethylene group reunion ethoxylations with the laurin of 30 oxyethylene group reunion ethoxylations; The fatty acid ester of sorb alcohol ether oxyethylation and/or oxypropylation (it can comprise 1 to 150 oxygen ethene and/or oxypropylene group) (especially C8-C24 acid, preferred C16-C22 acid); The dimethicone copolyol benzoic ether; Propylene oxide and multipolymer oxyethane are also referred to as the EO/PO polycondensate; And their mixture; The fatty acid ester of sugar ester and ether (for example sucrose stearate, sucrose cocounut oil acid esters and sorbitan monostearate and their mixture), polyvalent alcohol (especially glycerine or sorbyl alcohol) (C8-C24 for example, perhaps C16-C22 acid), for example stearin, stearin, laurin, Polyglycerine-2 stearate, Arlacel-65 or glycerine ricinoleate.

Anion surfactant comprises C16-C30 soap, for example derived from those of amine, and Triethanolamine Esters of Stearic Acid for example; The soap of polyoxyethylene, for example derived from those of amine or an alkali metal salt, and their combination; Phosphoric acid ester and salt thereof, for example for example PEG-5 citrate sulfo-succinic acid lauryl disodium and ricinoleic acid amide MEA sulfosuccinic ester disodium of oleth-10 phosphoric acid ester DEA salt or mono phosphoric acid ester cetyl one potassium sulfosuccinic ester; Sulfated alkyl ether, for example Zetesol NL; Isethionate; Acyl glutamate such as h-tallow disodium glutamate, alkyl polyglucoside and their combination.

Described emulsion can also comprise amphoterics; for example N-acylamino acid (as N-p dialkylaminobenzoic acid and cocounut oil acyl both sexes base oxalic acid disodium) and amine oxide (as the stearylamine oxide compound), or Silicon surfactant (for example dimethicone copolyol phosphoric acid ester).

Dyestuff

This emulsion can also comprise dyestuff.This dyestuff can be selected from powder dye (for example pigment and nacre) and water-soluble dye.For present patent application, term " pigment " means white or coloured, mineral or organic any type of particle, and it is insoluble to physiological medium, and it is intended to be used to making emulsion painted.For present patent application, term " nacre " means any type of iris particle, is especially produced in their shell by some mollusk, perhaps produces by synthetic.

Pigment can be white or coloured, and be mineral and/or organically.Mineral dye comprises titanium dioxide (optional through surface treatment), zirconium white or cerium oxide, zinc oxide, ferric oxide (black, yellow or redness), chromic oxide, manganese violet, ultramarine blue, chromium hydroxide, barba hispanica and metal powder (for example aluminium powder or copper powder).Pigment dyestuff comprises carbon black, D﹠amp; C type pigment and based on the color lake of cochineal or barium, strontium, calcium or aluminium.

Can also mention the resultful pigment of tool, the particle that for example comprises the base material (as glass, acrylic resin, polyester, urethane, polyethylene terephthalate, pottery or aluminum oxide) of natural or synthetic, organic or mineral, described base material is uncoated to be had or is coated with metallics, for example aluminium, gold and silver, platinum, copper or bronze, or be coated with metal oxide, for example titanium dioxide, ferric oxide or chromic oxide and their combination.

Nacre optional from white pearly pigment (as be coated with titanium or be coated with the mica of pearl white), coloured pearly pigment (as be coated with ferric oxide woddnite, be coated with barba hispanica or be coated with chromic oxide woddnite, be coated with the woddnite of the pigment dyestuff of the above-mentioned type) and based on the pearly pigment of pearl white.Select as another kind, can use coated interference pigment, for example liquid crystal or multi-coated interference pigment.

Structurizing reagent

This emulsion can also comprise structurizing reagent.For present patent application, term " structurizing reagent " means to increase the compound of the viscosity of this emulsion.Structurizing reagent makes the emulsion that might obtain to have from fluid to the solid quality.

With respect to the gross weight of emulsion, structurizing reagent can 0.1 % by weight to 20 % by weight, and perhaps the amount of 0.1 % by weight to 15 % by weight or 0.5 % by weight to 10 % by weight is present in emulsion.

This structurizing reagent can be selected from thickening material (oil medium thickening material, aqueous medium thickening material), organic gelling agent, wax, pasty state compound and natural gum.

the aqueous medium thickening material can be selected from: hydrophilic clay, hydrophilic fumed silica, water soluble cellulose base thickening material, guar gum, xanthan gum, carob glue, scleroglycan glue, gelling gum, sandlwood glue, kuteera gum or carrageenin, alginate, maltodextrin, starch and derivative thereof and hyaluronic acid and salt thereof, Polyglycerine (methyl) acrylic ester polymer of being sold by Hispano Quimica company or high Dean company (Guardian) with trade(brand)name Hispagel or Lubragel, Polyvinylpyrolidone (PVP), polyvinyl alcohol, crosslinked acrylamide polymer and multipolymer, perhaps crosslinked methacryloxyethyl trimethyl ammonium chloride homopolymer, association type polymkeric substance and especially association type urethane and sodium acrylate blend.This class thickening material has especially been described in patent application EP-A-1 400 234.

The oil medium thickening material can be selected from: close Organic clay; The hydrophobicity pyrolytic silicon dioxide; Alkyl guar gum (having the C1-C6 alkyl), those that for example describe in EP-A-708 114; Factice cohesion compound is for example by at least a monomer polymerization of ethylenic group or triblock polymer or the star polymer that copolymerization produces of containing.

Perhaps, structurizing reagent can be wax.For present patent application, term " wax " means to be under room temperature (25 ℃) lipophilic compound of solid, and it reversible solid-liquid state can occur changes, and it has the fusing point greater than or equal to 30 ℃, and fusing point can be up to 120 ℃.

Wax can be alkyl wax, fluorine wax and/or silicon wax, and can be plant, mineral, animal and/or synthetic origin.Particularly, described wax can have the fusing point higher than 30 ℃.

Suitable wax comprises beeswax, Carlow bar wax or gama wax, paraffin, Microcrystalline Wax, ceresin or ceresine; Synthetic wax, polyethylene wax or Fischer-Tropsch (Fischer-Tropsch) wax for example, and silicon wax, for example contain alkyl, alkoxyl group polydimethylsiloxane or the silsesquioxane resin wax as describing in Patent Application Publication WO2005100444 of 16 to 45 carbon atoms.

Perhaps, this emulsion can contain the pasty state compound, and it can be selected from lanolin and derivative thereof; Polymer-type or non-polymeric silicon compound; Polymer-type or non-polymeric fluoric compound; Vinyl polymer, the diene homopolymer of olefin homo, olefin copolymer, hydrogenation for example, and straight or branched oligopolymer, homopolymer or the multipolymer of (methyl) alkyl acrylate for example contain those of C8-C30 alkyl; The oligopolymer, homopolymer and the multipolymer that contain the vinyl ester of C8-C30 alkyl; The oligopolymer, homopolymer and the multipolymer that contain the vinyl ether of C8-C30 alkyl; One or more C2-C100(or C2-C50) polyether reactant between glycol, ester and their combination and the fat-soluble polyethers that produces.Described ester comprises the ester of glycerin oligomer, especially double glyceride, the condenses of hexanodioic acid and glycerine particularly, wherein some hydroxyls of glycerine with the mixture reaction of lipid acid (as stearic acid, capric acid, stearic acid and Unimac 5680 and 12-oxystearic acid).Phytogenous pasty state compound comprises mixture soyasterol and oxyethylation (5OE) oxypropylation (5OP) tetramethylolmethane.

Activeconstituents

" personal care promoting agent " used herein mean known in the art for usually add in personal care formulations with for the treatment of hair or skin with any compound of additive that beauty treatment and/or aesthstic beneficial effect are provided or the combination of compound.Any compound of pharmacy or medical science beneficial effect or the mixture of compound of providing known in the art is provided " health active agent ".Therefore, " health active agent " comprises that the material that is counted as activeconstituents or active pharmaceutical ingredient, these activeconstituentss or active pharmaceutical ingredient are normally used and define (specifically be included in the 21st piece of I chapter 200-299 part of CFR and 300-499 partly in) by U.S. sanitary and food and drug administration of Public services section.

Some representative example of activeconstituents comprise: medicine, VITAMIN, mineral; Hormone; The local biocide of using, antibiotic activity composition for example is used for the treatment of Active antifungal compound and the acne activeconstituents of sufficient moss, jock itch or psoriasis; The astringent matter activeconstituents; The reodorant activeconstituents; Remove wart agent activeconstituents; Corn and callosity remover activeconstituents; The pediculicide activeconstituents that is used for the treatment of head louse, crab louse (hair lice) and body louse; Be used for control head scurf, seborrheic dermatitis or psoriasic activeconstituents; And sunburn prevention and treatment agent.

The activeconstituents that can be used for described emulsion comprises VITAMIN and derivative thereof, comprises " pro-vitamin ".Can be used for VITAMIN of the present invention includes but not limited to: vitamin A ₁, Vogan-Neu, Vogan-Neu C2 to C18 ester, vitamin-E, tocopherol, the ester of vitamin-E and their combination.Vogan-Neu comprises trans-Vogan-Neu, 1,3-cis-Vogan-Neu, 11-cis-Vogan-Neu, 9-cis-Vogan-Neu and 3,4-, two dehydrogenations-Vogan-Neu, vitamins C and derivative thereof, vitamins B ₁, vitamins B ₂, former, the panthenol of vitamin B5, vitamins B ₆, vitamins B ₁₂, nicotinic acid, folic acid, vitamin H and pantothenic acid.consider to comprise in the present invention other suitable VITAMIN and international cosmetic raw material name (International Nomenclature Cosmetic Ingredient Name (the INCI)) name of described VITAMIN be called Vitamin C dipalmitate, xitix methyl-monosilane alcohol pectate, Quicifal, ascorbyl stearate, ascorbic acid glucoside, NAP, sodium ascorbate, xitix sulfuric ester disodium, (xitix/tocopherol) phosphoric acid ester potassium.

Perhaps, the activeconstituents for described emulsion can be active pharmaceutical ingredient.the representative example of more operable suitable active pharmaceutical ingredients is: hydrocortisone, Ketoprofen, timolol, pilocarpine, Zorubicin, ametycin, morphine, hydromorphone, Odizem, theophylline, Dx, daunorubicin, heparin, penicillin G, Pyocianil, Cephalothin, cefoxitin, cefotaxime, 5 FU 5 fluorouracil, cytosine arabinoside, the 6-azauridine, the 6-Tioguanine, vinealeucoblastine(VLB), vincristine(VCR), bleomycin sulfate, aurothioglucose, Suramine, Vermox, clonidine, Scopolamine, Proprasylyte, phenylpropanolamine hydrochloride, ouabain, coromegine, haloperidol, Isosorbide, pannonit, Ibuprofen BP/EP, ubiquinone, indomethacin, prostaglandin(PG), Naproxen Base, salbutamol, guanabenz, Trate, pheniramine, Trichlorphon and steroid.

Be considered as for this application active pharmaceutical ingredient comprise in the present invention be anti-acne agents such as benzoyl peroxide and vitamin A acid; Antiseptic-germicide such as chlorhexidine gluconate; Anti-mycotic agent such as miconazole nitrate; Anti-inflammatory agent; Corticosteroid medication; Non-steroidal anti-inflammatory agent such as diclofenac; The sick agent of psoriasis such as clobetasol propionate; Narcotic such as lignocaine; Pruritus; Anti-dermatitis agent; And the reagent that usually is considered as barrier film.

Perhaps, the activeconstituents in this emulsion can be protein, as enzyme.Enzyme includes but not limited to commercially available type, improvement type, recombinant type, wild-type, natural non-existent variant and their mixture.For example, suitable enzyme comprises lytic enzyme, at, oxydase, transferring enzyme, reductase enzyme, hemicellulase, esterase, isomerase, polygalacturonase, Sumylact L, peroxidase, laccase, catalase and their mixture.Lytic enzyme includes but not limited to: proteolytic enzyme (bacteria protease, fungal proteinase, aspartic protease, neutral protease or Sumizyme MP), amylase (α-amylase or β-amylase), lipase, mannonase cellulase, collagenase, N,O-Diacetylmuramidase, superoxide-dismutase, catalase and their mixture.Described proteolytic enzyme includes but not limited to: trypsinase, Quimotrase, stomach en-, pancreatin and other mammiferous enzymes; Papoid, bromeline and other plant enzyme; Subtilisin, epidermin, nisin, naringinase (L-rhamnosidase), urokinase and other bacterial enzymes.Described lipase includes but not limited to: triacylglycerol lipase, monoacylglycerol lipase, lipoprotein lipase, for example lipase of steapsin, erepsin, stomach en-, other mammals, vegetable lipase, bacterium lipase and purifying.Natural papoid can be used as described enzyme.In addition, stimulate hormone such as Regular Insulin can use to strengthen their effect together with these enzymes.

Perhaps, activeconstituents can be sun-screening agent.These sun-screening agents can be selected from any sun-screening agent that avoids being exposed to harmful effect of sunlight for the protection of skin known in the art.Sun-screening agent can be selected from organic compound, mineral compound or their combination that can absorb ultraviolet (UV) light.the representative non-limitative example that can be used as sun-screening agent comprises: benzaminic acid, cinoxate, the diethanolamine Methoxycinnamate, digalloyl trioleate, dioxybenzone, 4-[two (hydroxypropyl)] subcutin, glyceryl aminobenzoate, homosalate, the lawsone that contains otan, Sunburn preventive No. 2, Viosorb 930, octyl methoxycinnamate, octyl salicylate, Neo-Heliopan BB, padimate O, Phenylbenzimidazolesulfonic acid, red petrolatum, sulisobenzone, titanium dioxide and trolamine salicylate, acetaminophen, wallantoin PABA, benzal phthalide, benzophenone, benzophenone 1-12,3-α-tolylene camphor, the collagen sulphonamide of α-tolylene camphor hydrolysis, the α-tolylene camphorsulfonic acid, benzyl salicylate, bornelone, bumetrizole, PAROSOL 1789, butyl PABA, cerium oxide/silicon dioxide, the cerium oxide/silicon dioxide talcum, cinoxate, the DEA-Methoxycinnamate, dibenzo oxazole naphthalene, di-t-butyl phenol methylene camphor, digalloyl trioleate, di-isopropyl tolyl acrylic acid ester, dimethyl PABA ethyl cetearyl Dimethyl Ammonium tosylate, UVASORB HEB, phenylbenzene methoxy formyl radical acetoxyl group aphthopyrans, two ethylbenzene triamino triazine Stilbene disulfonic acid disodiums, distyryl phenylbenzene triamino triazine Stilbene disulfonic acid disodium, distyryl phenylbenzene disulfonic acid disodium, drometrizole, Ethylhexysalicylate, ethyl dihydroxypropyl PABA, ethyl di-isopropyl laurate, the ethyl Methoxycinnamate, ethyl PABA, the urocanic acid ethyl ester, the forulic acid etocryene, glycerine ethylhexoate dimethoxy-cinnamic acid ester, glyceryl PABA, the ethylene glycol salicylate, homosalate, Neo Heliopan E1000, the isopropyl benzyl salicylate, isopropyl diphenyl formyl methane, the sec.-propyl Methoxycinnamate, the menthyl anthranilate, the menthyl salicylate, 4-methyl benzylidene, camphor, Viosorb 930, Octrizole, octyldimethyl PABA, octyl methoxycinnamate, octyl salicylate, UVINUL T-150 PABA, PEG-25 PABA, the amyl group dimethyl PABA, Phenylbenzimidazolesulfonic acid, the polyacrylamide methyl benzylidene camphor, methoxy cinnamic acid potassium, Phenylbenzimidazolesulfonic acid potassium, red petrolatum, Phenylbenzimidazolesulfonic acid sodium, urocanic acid sodium, TEA-Phenylbenzimidazolesulfonic acid salt, the TEA-salicylate, the Terephthalidene Dicamphor Sulfonic Acid, titanium dioxide, zinc oxide, cerium dioxide, three PABA panthenols, urocanic acid and VA/ crotonate/methacryloxypropyl BP-1 multipolymer.These sun-screening agents can be selected in one or both or more kinds of combinations.

Perhaps, described activeconstituents can be plant milk extract.Perhaps, activeconstituents can be imitative suntan such as but not limited to otan and erythrulose, or wormer is such as but not limited to butyl acetylamino ethyl propionate, or plant milk extract such as pamorusa oil.The amount of the activeconstituents that exists in this emulsion will depend on many factors (comprising the type of selected activeconstituents and the using method of described emulsion) and change, yet, with the weighing scale of emulsion, the amount of activeconstituents can be 0.05 % by weight to 50 % by weight or 1 % by weight to 25 % by weight or 1 to 10 % by weight.

Perhaps, activeconstituents can be antiperspirant and/or reodorant.some examples of antiperspirant and reodorant are: aluminum chloride, the aluminum-zirconium tetrachlorohydrex GLY coordination compound, aluminum zirconium tetrachlorohydrate PEG coordination compound, chlorination hydroxyl aluminum binary alcohol coordination compound, aluminum zirconium tetrachlorohydrate PG coordination compound, chlorination hydroxyl aluminium PEG coordination compound, trichlorine hydroxyl aluminium zirconium, chlorination hydroxyl aluminium PG coordination compound, trichlorine hydroxyl aluminium zirconium GLY coordination compound, Hexachlorophene, benzalkonium chloride, sesquialter chlorination hydroxyl aluminium, sodium bicarbonate, sesquialter chlorination hydroxyl aluminium PEG coordination compound, CHLOROPHYLLINE-copper complex, triclosan, eight chlorine hydroxyl aluminium zirconium and zinc ricinoleates.

Perfume compound

Perfume compound or spices also can be added into this emulsion.Perfume compound can be any spices and the perfume compound that is generally used in fragrance industry.These perfume compound compositions can belong to the number of chemical classification, and are as of all kinds in the compound of alcohol, aldehyde, ketone, ester, ether, acetic ester, nitrous acid ester, terpenes hydrocarbon, heterocyclic nitrogen containing or sulphur and the essential oil of natural origin or synthetic origin etc.Many these perfume compound compositions are at textbook reference such as the Perfume and Flavour Chemicals of standard, 1969, S.Arctander, Montclair, N.J.(" spices and aromachemicals ", 1969, S.Arctander, the Montclair, New Jersey you) in be described.

Sanitas

When the emulsifying agent of describing with the present invention prepares emulsion, it may be desirable adding Determination of Preservatives, for example metagin, BHT, BHA, phenoxyethyl alcohol are as the appendix VI part 1 of European Union's makeup instruction-LIST OF PRESERVATIVES WHICH COSMETIC PRODUCTS MAY CONTAIN(" list of the sanitas that makeup can contain ") upper listed.When existing, with the weighing scale of emulsion, the amount of sanitas can be 0.01 % by weight to 5 % by weight.

This emulsion is applicable to the personal care product.this class personal care product's example has antiperspirant and reodorant, protective skin cream, the skin care lotion, wetting Agent for Printing Inks, facial treatment agent is as removing acne agents or winkle removing agent, personal cleanser and facial cleansing agent, bathe oil, perfume, Gulong perfume, face powder, sun-screening agent, the front use that shaves and the rear lotion of using that shaves, shaving soap and shaving foam, shampoo, hair conditioner, hair coloring agents, hair is straight along agent, hair jelly, mousse, gelifying agent, agent for permanent hair waving, trichogen and stratum corneum coating, makeup, color make-up, foundation cream, hide free time cream, kermes, lipstick, eyeliner, Mascara, removers, the color make-up remover, the wrinkle weighting agent, skin defect is hidden agent, the skin surface smooth agent, the eyelash curler herbal leaven, nail varnish, the hair cosmetic product, eye shadow, health cosmetic agent, and pulvis, medicine frost cream, paste or sprays (comprise anti-acne agents, the tooth hygiene agent, microbiotic, accelerator for concrescence, nutrition agent etc., it can be preventative and/or curative).

Example

Comprise that following example is to show the present invention to those of ordinary skill.Yet, according to the disclosure, will be understood by those skilled in the art that, can make many changes and still can obtain similar or identical result and not break away from the spirit and scope of the present invention in disclosed specific embodiment.Except as otherwise noted, otherwise all quantity, ratio and per-cent all by weight.

Example 1 – multipolymer preparation

295.6g DOW packs in the 1000ml flask that is equipped with Dean-Stark trap, reflux exchanger, temperature regulator and heating mantles and agitator Polydimethylsiloxane, 44.7g DOW that 4-2737 is silanol stopped

5cSt 200 liquid, 233.2g derive from the octadecane methyl dimethoxysilane of Gai Lesi peculiar limit company (Gelest, Inc.) and the aminopropyl methyldiethoxysilane that 11.5g derives from Sigma aldrich company (Sigma Aldrich).This of Multiple components is combined in heating under 80 ℃, then adds 0.9g KOH in the gained mixture, and start nitrogen purging in whole reactor.After two hours, add 7g water, continue to stir two hours.When the condensation in the Dean-Stark trap stops, then add 7g water, and with mixture heating up to 120 ℃.After 2 hours, stop nitrogen gas stream, and while stirring with mixture heating up to 150 ℃.After 4 hours, mixture is cooled to 70 ℃, then adds the 0.96g Glacial acetic acid.In next step, vacuumize 4 hours to remove volatile matter under 150 ℃.The gained mixture is cooled to 70 ℃, and then the strainer by 0.45 micron pore size filters to obtain alkyl-modified aminosiloxane.

Then the 200g abovementioned alkyl aminosiloxane of packing in the 1000ml flask adds 3.66g δ-glucono-lactone and 203.66g Virahol.Mixture was heated 4 hours under 74 ℃.After 4 hours, remove Virahol by carry out coupling vacuum stripping under 74 ℃.

Example 2 – multipolymers are synthetic

Repeat example 1, different is is being incorporated under 74 ℃ heating and is adding oil after 4 hours again alkylamino siloxanes, δ-glucono-lactone and Virahol are mixed.After adding oil, remove Virahol by carry out coupling vacuum stripping under 74 ℃.Used oil is 5cSt 200 liquid, and its consumption is enough to prepare 25% the combination from the oil of the multipolymer of example 1 and 75%.

Example 3 and 4 – multipolymers are synthetic

Repeat example 1 and 2, different is to synthesize to carry out with the stoichiometric amount less than δ-glucono-lactone in second step, so second step is carried out following modification.

The 200g abovementioned alkyl aminosiloxane of packing in the 1000ml flask, then pack into 1.83g δ-glucono-lactone and 201.83g Virahol.Mixture was heated 4 hours under 74 ℃.After 4 hours, selectively add oil.Remove alcohol by carry out coupling vacuum stripping under 74 ℃ in vacuum.For example 3, oily to add before removing Virahol in coupling vacuum stripping.For example 4, used oil is 5cSt200 liquid, and its consumption is enough to prepare 25% the combination from the oil of the multipolymer of example 1 and 75%.

Example 5 and 6 – multipolymers are synthetic, end-blocking

Make the multipolymer of preparation in example 3 and 4 stand termination procedure.End-blocking is undertaken by following operation: pack in each 1000ml flask multipolymer of 200g example 3 or the multipolymer of above-mentioned example 4/oil combination.Add following composition to each flask: 2.78g dodecyl/tetradecyl glycidyl ether and 202.78g Virahol.Mixture was heated 8 hours under 74 ℃, then by removing Virahol with vacuum 74 ℃ of lower coupling vacuum stripping.

Example 7 and 8 – consistencies

Prepare two kinds of multipolymers by the method that repeats example 1.Every kind of multipolymer has formula:

Wherein subscript y is 0.75, and subscript x is 65, subscript z be 10 and subscript n be 16.

Comparative example 9 – consistencies

Relatively the sugared siloxanes of use prepares in being equipped with the 500ml flask of agitator, reflux exchanger and temperature regulator, and preparation method is: mix 100g trimethylsiloxy end-blocking poly-(dimethyl/methyl (aminoethylamino isobutyl-) siloxanes) (DP be 44 and per molecule have average 2.57 aminoethylamino isobutyl-functional groups) and 6.61g δ-glucono-lactone.Then add 106.6g ethanol, this mixture is reacted under 74 ℃.After reaction four hours, add 40.12g dodecyl/tetradecyl glycidyl ether and reacted 8 hours.After reaction is completed, remove ethanol by carry out stripping under 74 ℃ in vacuum.

The reaction scheme of second step is as follows.

Confirm structure in top reaction scheme with H-NMR.

Comparative example 10 – consistencies

In order to compare, used commercially available emulsifying agent, namely from the win of Virginia, USA Hopewell wound Gao Shi Mitt USA Corporation (Evonik Goldschmidt Corporation (Hopewell, Virginia, U.S.A.)) EM 90(hexadecyl polyoxyethylene glycol, the functionalized polydimethylsiloxane of polypropylene glycol).

Example 7 and 8 and comparative example 9 and 10 in, multipolymer is dispersed in various oil to determine consistency.In every duplicate samples, mix 9 gram oil and 1g multipolymers under envrionment conditions.Result provides in table 1.

Table 1: compatibility test result

In table 1,5cSt 200 liquid refer to can be used as DOW

The viscosity that 200 liquid derive from Dow Corning Corporation (Dow Corning Corporation) is the polydimethylsiloxane of 5 centistokes, and FZ-3196 refers to derive from the polydialkysiloxane liquid of Dow Corning Corporation (Dow Corning Corporation).

Emulsion example 11 to 18-prepares the method for emulsion with stirring mixer

Preparation uses multipolymer as the emulsion that contains the composition in table 2 of emulsifying agent by the following method.

1. the composition with phase A mixes to obtain homogenizing mixture.

2. the composition with phase B mixes to obtain homogenizing mixture.

3. under agitation (with intersecting agitator) is added into phase A with phase B.When adding phase B, mixing velocity increases to 1000rpm from 700rpm.

4. after adding whole phase B, the product of gained was mixed 1 minute with 1000rpm and mixed 5 minutes with 2000rpm.Obtain thick emulsion.

5. make the 100 thick samples of latex of gram by high shear mixing equipment 15 seconds to reduce granularity.This high shear mixing equipment is the laboratory stirrer from English Silverson Mechanology Inc. (Silverson Machines Ltd. (England)).Obtain miniemulsion.

The multipolymer that derives from example 1 has following formula:

Wherein subscript M is 0.75, and subscript N is 65, and subscript O is 10.

The method for preparing emulsion with the dentistry mixing tank

Can prepare by the following method and use multipolymer as the emulsion of emulsifying agent.

1. the composition with phase A mixes.

2. the composition with phase B mixes.

3. add phase B to phase A with the 5g increment.

4. after adding each increment, with products therefrom at dentistry mixing tank (DAC 150 Xi Lie – SpeedMixer ^TM) in mixed 40 seconds with 3400rpm.

5. repeating step 3 and 4 is until added all phase B to obtain final emulsion.

With reference to Shi Li – stability of emulsion

By the sample of each emulsion being stored the stability of the emulsion 11 to 18 of assessing this paper preparation over 6 months under room temperature (RT), 40 ℃ and 50 ℃.By the range estimation measurement stability.Provide in result table 2 below.

Freeze/melt stability with reference to Shi Li – emulsion

Stability is frozen/is melted in sample evaluation to the emulsion 11 to 18 of the present invention preparation.Program is as follows:

1. with samples of latex under 4 ℃ freezing minimum 12 hours, then at room temperature preserve a few hours.

2. evaluation stability of emulsion.By the range estimation measurement stability.

3. step 1 and 2 is repeated five times.Provide in result table 3 below.

Industrial usability

Above-mentioned multipolymer can be used as the emulsifying agent of water-in-oil (w/o) type emulsion (particularly wherein said oil comprises silicon).Alternatively, above-mentioned multipolymer can be used as the w/o type emulsion emulsifying agent of (wherein said oil includes machine oil).This multipolymer can provide and have low smell the emulsion of (namely compare with the emulsion that contains silicon polyethers emulsifying agent, have low smell).This multipolymer also can provide the non-irritating emulsion of skin, and the personal care product of namely containing the emulsion that contains this multipolymer of safe and effective amount is suitable for application to skin.

Claims (35)

1. sugared silicone copolymers, described multipolymer has following formula:

R ² _aR ¹' _a’R ¹ _{(3-a-a ')}SiO-[(SiR ²R ¹O) _m-(SiR ¹ ₂O) _n(SiR ¹' R ¹O) _o] _y-SiR ¹ _{(3-a-a ')}R ¹' _a’R ² _aWherein

Each R ¹Can identical or different and each R ¹The alkyl, organic group or the formula R that comprise hydrogen, 1 to 12 carbon atom ³-Q group;

Q comprises epoxy group(ing), cycloalkyl epoxy base, primary amine or secondary amine, quadrol, carboxyl, halogen, vinyl, allyl group, acid anhydrides or mercapto functional group;

Each R ¹' for having the unit price organic group of average at least 13 member's atoms;

Subscript m has the mean value in 0 to 10,000 scope;

Subscript n has the mean value in 0 to 10,000 scope;

Subscript m, n and o can be identical or different;

Subscript o has the mean value in 0 to 10,000 scope;

Each subscript a is 0,1,2 or 3 independently;

Each subscript a ' is 0,1,2 or 3 independently;

Subscript y makes described multipolymer have integer lower than 100 ten thousand molecular weight, and the value of subscript y is at least 1;

Each R ²Has formula Z-(G ¹) _b-(G ²) _c, and each copolymer molecule on average has at least one R ², wherein

G ¹For comprising the sugar component of 5 to 12 carbon atoms,

Amount (b+c) has the value of scope 1 to 10, and

Subscript b or subscript c can be 0,

G ²For comprising in addition by the sugar component of 5 to 12 carbon atoms of organic radical or organic silica-based replacement,

Each Z is for connecting base and being independently selected from:

-R ³-NHC(O)-R ⁴-、

-R ³-NHC(O)O-R ⁴-、

-R ³-NH-C(O)-NH-R ⁴-、

-R ³-C(O)-O-R ⁴-、

-R ³-O-R ⁴-、

-R ³-CH(OH)-CH ₂-O-R ⁴–、

-R ³-S-R ⁴-、

-R ³-CH(OH)-CH ₂-NH-R ⁴-、

-R ³-N(R ¹)-R ⁴-、

-NHC(O)-R ⁴-、

-NHC(O)O-R ⁴-、

-NH-C(O)-NH-R ⁴-、

-C(O)-O-R ⁴-、

-O-R ⁴-、

-CH(OH)-CH ₂-O-R ⁴–、

-S-R ⁴-、

-CH(OH)-CH ₂-NH-R ⁴-、

-N(R ¹)-R ⁴-、

-R ³-NHC(O)-、

-R ³-NHC(O)O-、

-R ³-NH-C(O)-NH-、

-R ³-C(O)-O-、

-R ³-O-、

-R ³-CH(OH)-CH ₂-O–、

-R ³-S-、

-R ³-CH(OH)-CH ₂-NH-、

-R ³-N(R ¹)-、

-R ³-N(R ⁸)-C(O)-R ⁴-、

-R ³-CH (OH)-CH ₂-N (R ⁸)-R ⁴-or

-R ³-CH(N(R ⁴)(R ⁸))CH ²OH；

Each R wherein ³With each R ⁴To comprise formula (R ⁵) _r(R ⁶) _s(R ⁷) _tThe divalence spacer groups of group,

Wherein at least one in subscript r, s and t is 1, and

Each R ⁵With each R ⁷The alkylidene group of 1 to 12 carbon atom independently;

Each R ⁶Wei – N (R ⁸)-, be R wherein ⁸Be selected from R ³, formula Z-X group, univalence hydrocarbyl or – N (H)-with the reaction product of epoxy-functional, cycloalkyl epoxy functional group, glycidyl ether functional group, anhydride functional group or lactone;

Each X is dibasic carboxylic acid, phosphate radical, sulfate radical, sulfonate radical or quaternary ammonium group independently, and

Precondition is

R ³And R ⁴In at least one must be present in described connection base, and

Each R ³With each R ⁴Can be identical or different.

2. multipolymer according to claim 1, wherein each Z is independently selected from :-R ³-N (R ⁸)-C (O)-R ⁴-,-R ³-CH (OH)-CH ₂-N (R ⁸)-R ⁴-, perhaps

-R ³-CH(N(R ⁴)(R ⁸))CH ₂OH。

3. according to claim 1 or multipolymer claimed in claim 2, wherein subscript m and n are from 0 to 500 integer and can be identical or different.

4. according to claim 1 or multipolymer claimed in claim 2, wherein subscript o is from 0 to 2,500 integer.

5. method for the preparation of the described sugared silicone copolymers of any one according to claim 1 to 4, wherein said method comprises the steps:

I) make the organopolysiloxane of functional organic and sugar moieties react to prepare described sugared silicone copolymers under the existence of solvent;

Randomly, ii) remove the part of described solvent: and

Randomly, iii) interpolation is oily.

6. method according to claim 5, wherein said oil is in step I) before and/or step I) during add.

7. method according to claim 5, wherein said oil is at step I i) during and/or at step I i) add afterwards.

8. method according to claim 5, also comprise iv) remove described solvent.

9. method for the preparation of the described multipolymer of any one according to claim 1 to 4, described method comprises:

1) balance of following ingredients and/or condensation reaction

I) organopolysiloxane of short chain silanol functional,

Ii) amino dialkoxy alkyl silane,

Iii) dialkyl dialkoxy silicane is wherein R at least one of described the above alkyl of dialkyl dialkoxy silicane ¹', and

Iv) end blocking agent; And

2) make step 1) product and sugar lactone reaction.

10. method according to claim 9, wherein said sugar lactone is the glyconic acid lactone.

11. according to claim 9 or method claimed in claim 10, also comprise making step 2) the step 3 of product and the end-capping reagent reaction that is selected from lactone, halo unsaturated compound, epoxy functional compounds or acid anhydrides).

12. method according to claim 11, wherein step 3) in described lactone be selected from: butyrolactone, 6-caprolactone, γ-glucono-lactone, δ-glucono-lactone and lactobionic acid lactone.

13. method according to claim 11, wherein said halogenation unsaturated compound is thiazolinyl chlorine.

14. method according to claim 11, wherein said epoxy functional compounds are selected from allyl group epoxy functional compounds, cycloalkyl epoxy functional compound, glycidyl ether functional compound and Racemic glycidol.

15. method according to claim 11, wherein said acid anhydrides comprise diacetyl oxide, sym-dichloroacetic anhydride, propionic anhydride, crotonic anhydride, methacrylic anhydride, butyryl oxide, isobutyric anhydride, diethylpyrocarbonate or 4-pentenoic acid anhydride.

16. method according to claim 5, wherein step I) react to carry out by making each composition, described composition comprises:

(A) organopolysiloxane of aminofunctional, and

(B) sugar lactone.

17. method according to claim 5, wherein step I) react to carry out by making each composition, described composition comprises:

(A) organopolysiloxane of epoxy-functional, and

(B) N-alkylated glucamine.

18. method according to claim 5, wherein step I) undertaken by the method that comprises the steps:

1) make (a) N-alkylated glucamine and (b) the epoxy compounds reaction of alkenyl functional, and

2) make step 1) product and (c) poly-organic radical hydrogen siloxane generation addition reaction of silicon with hydrogen.

19. method according to claim 18, step I wherein) product contains secondary amine functional groups, and described method also comprises makes step I) the step of product and the end-capping reagent reaction that is selected from lactone, halo unsaturated compound, epoxy functional compounds or acid anhydrides.

20. wherein there is described solvent in method according to claim 5, and described solvent is the alcohol that is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, 2-propyl alcohol, isopropylcarbinol, propyl carbinol and their combination.

21. wherein there is described oil in method according to claim 5, and described oil is silicone oil.

22. method according to claim 21, wherein said oil is polydialkysiloxane.

23. wherein there is described oil in method according to claim 5, and described oil is the organic oil that is selected from hydrocarbon ils, ester, vegetables oil, mineral oil or Fatty Alcohol(C12-C14 and C12-C18).

24. method according to claim 5, wherein said multipolymer and described oil are so that the weight ratio of multipolymer/oil is 1/1 to 1/50 amount existence.

25. a composition comprises:

(A) the described multipolymer of any one according to claim 1 to 4, and

(B) other composition.

26. composition according to claim 25, wherein composition (B) comprising:

(ii) be suitable for allowing the part to apply composition in the mounting medium of the part of health,

(iii) linking agent,

(iv) tensio-active agent, or

(v) their combination.

27. wherein there is composition (iii) in composition according to claim 26, and composition (iii) comprises water.

28. composition according to claim 27, wherein said composition is emulsion.

29. the described composition of any one according to claim 25 to 28, wherein said composition is the personal care composition that is adapted to provide for the part of its described health that puts on beneficial effect.

30. an emulsion comprises:

A) discontinuous water,

B) continuous oil phase, and

C) emulsifying agent, wherein said emulsifying agent comprise the described multipolymer of any one according to claim 1 to 4.

31. the method for the preparation of emulsion according to claim 30 comprises:

1) described emulsifying agent is dispersed in described oil phase,

2) described water is added in described oil phase, and

Randomly, 3) make step 2) product stand shearing force.

32. a composition comprises:

I) emulsion according to claim 30, and

II) additive.

33. composition according to claim 32, composition II wherein) be selected from: other silicon, aerosol, antioxidant, sanitising agent, tinting material, other amendment, precipitation agent, ionogen, softener and oil, exfoliator, profoamer, perfume compound, wetting agent, sealing agent, pediculicide, the pH control agent, pigment, sanitas, biocide, other solvents, stablizer, sun-screening agent, suspending agent, tanning agent, other tensio-active agents, thickening material, VITAMIN, plant-based medicine, wax, rheology modifier, antiperspirant, antidandruff agent, anti-acne agents, anti-caries agent and wound healing promotor, oil in addition, hydrophilic medium, weighting agent, fiber, film-forming polymer, other tensio-active agent and/or emulsifying agent, dyestuff, structurizing reagent, activeconstituents, perfume compound, sanitas, and their combination.

34. composition according to claim 33, wherein said composition are the personal care compositions that is adapted to provide for the part of its described health that puts on beneficial effect.

35. composition according to claim 34, wherein said personal care composition is selected from antiperspirant and reodorant, protective skin cream, the skin care lotion, wetting Agent for Printing Inks, facial treatment agent is as removing acne agents or winkle removing agent, personal cleanser and facial cleansing agent, bathe oil, perfume, Gulong perfume, face powder, sun-screening agent, the front use that shaves and the rear lotion of using that shaves, shaving soap and shaving foam, shampoo, hair conditioner, hair coloring agents, hair is straight along agent, hair jelly, mousse, gelifying agent, agent for permanent hair waving, trichogen and stratum corneum coating, makeup, color make-up, foundation cream, hide free time cream, kermes, lipstick, eyeliner, Mascara, removers, the color make-up remover, the wrinkle weighting agent, skin defect is hidden agent, the skin surface smooth agent, the eyelash curler herbal leaven, nail varnish, the hair cosmetic product, eye shadow, health cosmetic agent, and pulvis, medicine frost cream, paste or sprays comprise anti-acne agents, the tooth hygiene agent, microbiotic, accelerator for concrescence, nutrition agent etc., it can be preventative and/or curative.